Thermosetting compositions and forming three-dimensionalobjects therefrom

ABSTRACT

Thermoset compositions and methods for forming three-dimensional articles via an additive fabrication process, and articles made therefrom are disclosed herein. In an embodiment, a composition comprises a first network-forming component comprising a TPA-based polyester comprising a backbone and having at least 2 polymerizable groups, one or more first network monomers, and a first network initiator. The backbone of the TPA-based polyester comprises the reaction product of a terephthalic acid and a polyol. The composition may further comprise a second network-forming component.

FIELD

The invention relates to thermosetting compositions and methods forproducing three-dimensional objects by additive fabrication techniques,and articles produced therefrom.

BACKGROUND

Additive fabrication, also known as three-dimensional printing, is atechnique for forming three-dimensional objects from computer data bybuilding up objects one portion at a time until a finalthree-dimensional object is produced. Additive techniques can becontrasted with subtractive techniques, such as milling, whereinportions of material are removed from a larger amount of material toproduce the final three-dimensional object.

Various types of materials are used in additive fabrication processes.Generally, thermoplastic materials are used in, for example fusedfilament fabrication (FFF) and selective laser sintering (SLS)processes, whereas thermoset materials are used in, for example vatbased processes and processes that involve jetting of liquid materials.

Generally, electromagnetic radiation is used to encourage rapid curingof the thermosetting materials. The electromagnetic radiation may be UV,visible, or infrared light and may be applied, for example, by lasers,lamps, or LEDs. The electromagnetic radiation may be appliedselectively, e.g. by drawing a specific pattern with a laser, using adigital micromirror device (DMD), or a mask, or unselectively, e.g. bypassing a lamp over the entirety of a surface. Post-processing byapplying additional temperature or light to the newly formedthree-dimensional object may be necessary to achieve the desiredproperties of a three-dimensional object formed from a thermosettingcomposition.

Various advances have been made to thermosetting materials for additivefabrication to improve the mechanical properties of the finishedarticle. For example, US2010/0304088 describes a radiation curable resincomposition comprising cationically polymerizable components and animpact modifier that, after full cure, results in a material having ahigh tensile modulus and high toughness, as shown by high impactstrength and/or high resistance against crack propagation.

In US2011/0104500, there is described a radiation curable resin that,upon cure, attains a desirable combination of modulus, impact strength,heat deflection temperature, and water absorption. The radiation curableresin comprises a combination of epoxy functional components, an oxetanecomponent, a (meth) acrylate component, an impact modifier, afree-radical photo-initiators, and a cationic photo-initiator.

Although various advances have been made to thermosetting materials foradditive fabrication in recent years, the industry continues to demandbetter mechanical properties. An example of a material that has not yetbeen realized is a photo-polymerizable material that simultaneouslyachieves high glass transition temperature (Tg) and high toughness.

SUMMARY

The invention employs a polyester comprising i) a backbone comprisingthe reaction product of a terephthalic acid (TPA) and a polyol, and ii)a number average of at least two polymerizable groups per molecule,wherein the polymerizable groups comprise acrylate, methacrylate, epoxy,oxetane, hydroxyl, itaconate, vinyl ether, allyl ether, maleate, orfumarate (hereinafter, “TPA-based polyester”). The TPA-based polyesterhas a number average molecular weight of from 800 to 10,000 g/mol and aglass transition temperature (Tg) of 40° C. or more. The TPA-basedpolyesters may be employed in compositions, such as compositions forforming a three-dimensional object via an additive fabricationprocesses, or as a kit of materials, which forms a composition when theelements of the kit of materials are combined.

In an embodiment, the TPA-based polyester is present in a composition aspart of a first-network forming component consisting of 19.95 to 80 wt %of the TPA-based polyester, 19.95 to 80 wt % of one or more firstnetwork monomers having a number average of 0.95 to 1.1 polymerizablegroups, 0.05 to 5 wt % of one or more first network-forming initiators,and, optionally, up to 15 wt % of one or more further first network,monomers, oligomers, or polymers having a number average of 2 or morepolymerizable groups. The substituents of the first network-formingcomponent are able to (co)polymerize with the polymerizable groups ofthe TPA-based polyester and/or the one or more first-network monomers.If a component of the polymerizable composition cannot (co)polymerizewith any of the first network-forming components then the componentcannot be a first network-forming component. Particulate fillers thatcomprise polymerizable groups that are able to (co)polymerize with thepolymerizable groups of the TPA-based polyester are not part of thefirst network-forming component.

An optional second network-forming component may be present in thecomposition. The second network-forming component comprises one or moresecond network compounds that comprise polymerizable groups that do not(co)polymerize with the polymerizable groups of the TPA-based polyester,and a second network initiator for initiating polymerization of the oneor more second network compounds.

The components of the composition may also be separated and provided asa kit of materials. Further embodiments of the invention are describedbelow.

DETAILED DESCRIPTION

The composition for forming a three-dimensional object via an additivefabrication process comprises at least a first network-formingcomponent. In an embodiment, the composition for forming athree-dimensional object via an additive fabrication process consists ofa first network-forming component.

The first network-forming component comprises at least a TPA-basedpolyester, one or more first network monomers, and a first networkinitiator. In an embodiment, the first network-forming componentconsists of at least a TPA-based polyester, one or more first networkmonomers, and a first network initiator. The TPA-based polyester shouldbe soluble in the one or more first network monomers, such that, whenmixed together, the parts of the first network-forming component shouldbe present as a clear liquid.

In an embodiment, the first network-forming component is present in anamount of 20 wt % or more, 25 wt % or more, 30 wt % or more, 35 wt % ormore, 40 wt % or more, 50 wt % or more, 60 wt % or more, 70 wt % ormore, 80 wt % or more, 90 wt % or more, 95 wt % or more, or 100 wt %,based on the total weight of the composition. In an embodiment the firstnetwork-forming component is present in an amount of 100 wt % or less,90 wt % or less, 80 wt % or less, 70 wt % or less, or 60 wt % or less,based on the total weight of the composition.

In an embodiment, the first network-forming component is present in anamount of 20 wt % or more, 25 wt % or more, 30 wt % or more, 35 wt % ormore, 40 wt % or more, 50 wt % or more, 60 wt % or more, 70 wt % ormore, 80 wt % or more, 90 wt % or more, 95 wt % or more, or 100 wt %,based on the total weight of the composition, excluding the weight ofany solvent. A solvent is a non-reactive liquid in which the componentsof the composition are dissolved. Typically, solvents are low molecularweight alcohols or water, depending on the reactive functionality of thecomposition. In an embodiment the first network-forming component ispresent in an amount of 100 wt % or less, 90 wt % or less, 80 wt % orless, 70 wt % or less, or 60 wt % or less, based on the total weight ofthe composition excluding any solvent.

In an embodiment, the first network-forming component is present in anamount of 20 wt % or more, 25 wt % or more, 30 wt % or more, 35 wt % ormore, 40 wt % or more, 50 wt % or more, 60 wt % or more, 70 wt % ormore, 80 wt % or more, 90 wt % or more, 95 wt % or more, or 100 wt %,based on the weight of the composition, excluding the weight of anysolvent and the weight of any components that do not comprise apolymerizable group (e.g. a non-reactive particulate filler). In anembodiment the first network-forming component is present in an amountof 100 wt % or less, 90 wt % or less, 80 wt % or less, 70 wt % or less,or 60 wt % or less, based on the total weight of the compositionexcluding any solvent and any components that do not comprise apolymerizable group.

Optionally, the composition additionally comprises one or more furtherfirst network monomers, oligomers, or polymers having a number averageof 2 or more polymerizable groups that are able to (co)polymerize withthe polymerizable groups of the TPA-based polyester or the one or morefirst-network monomers.

Optionally, the composition additionally comprises a secondnetwork-forming component comprising one or more second networkcompounds that do not (co)polymerize with the first network-formingcomponent, and a second network initiator for initiating thepolymerization of the one or more second network compounds. For example,the first network-forming component may be polymerizable by free-radicalpolymerization and the second network-forming component may bepolymerizable by cationic polymerization.

For purposes of the instant application, a non-limiting list of groupsthat (co)polymerize or do not (co)polymerize are defined as follows.Acrylate, methacrylate, itaconate, allyl ether, maleate, or fumarategroups (co)polymerize with acrylate, methacrylate, itaconate, vinylether, allyl ether, maleate, or fumarate groups, and do not(co)polymerize with hydroxyl, epoxy, and oxetane groups. Hydroxyl,epoxy, and oxetane groups (co)polymerize with hydroxyl, epoxy, oxetane,and vinyl ether groups, and do not (co)polymerize with acrylate,methacrylate, itaconate, allyl ether, maleate, or fumarate groups. Vinylether groups (co)polymerize with acrylate, methacrylate, epoxy, oxetane,hydroxyl, itaconate, vinyl ether, allyl ether, maleate, or fumarategroups.

Thus, in the case that the TPA-based polyester comprises a numberaverage of at least 2 acrylate, methacrylate, itaconate, allyl ether,maleate, or fumarate groups per molecule, the one or more first networkmonomers comprise an acrylate, methacrylate, itaconate, vinyl ether,allyl ether, maleate, or fumarate group and the optional one or morefurther first network monomers, oligomers or polymers comprises a numberaverage of 2 or more acrylate, methacrylate, itaconate, vinyl ether,allyl ether, maleate, or fumarate groups. In the case that the TPA-basedpolyester comprises a number average of at least 2 hydroxyl, epoxy, oroxetane groups per molecule, the one or more first network monomerscomprise a hydroxyl, epoxy, oxetane, or vinyl ether group and theoptional one or more further first network monomers, oligomers orpolymers comprises a number average of 2 or more hydroxyl, epoxy,oxetane, or vinyl ether groups. In the case that the TPA-based polyestercomprises a number average of at least 2 vinyl ether groups permolecule, the one or more first network monomers comprise an acrylate,methacrylate, itaconate, hydroxyl, epoxy, oxetane, vinyl ether, allylether, maleate, or fumarate group and the optional one or more furtherfirst network monomers, oligomers or polymers comprises a number averageof 2 or more acrylate, methacrylate, itaconate, hydroxyl, epoxy,oxetane, vinyl ether, allyl ether, maleate, or fumarate groups.

In an embodiment, the TPA-based polyester comprises multiple differenttypes of polymerizable groups. In an embodiment, the TPA-based polyestercomprises a combination of methacrylate and acrylate groups. In anembodiment, the TPA-based polyester comprises a free-radicallypolymerizable group and a cationic polymerizable group. In anembodiment, the TPA-based polyester comprises i) at least onepolymerizable group selected from acrylate, methacrylate, itaconate,allyl ether, maleate, or fumarate, and ii) at least one polymerizablegroup selected from hydroxyl, epoxy, or oxetane. In the case where theTPA-based polyester comprises i) at least one polymerizable groupselected from acrylate, methacrylate, itaconate, allyl ether, maleate,or fumarate, and ii) at least one polymerizable group selected fromhydroxyl, epoxy, or oxetane, the one or more first network monomerscomprise an acrylate, methacrylate, itaconate, hydroxyl, epoxy, oxetane,vinyl ether, allyl ether, maleate, or fumarate group and the optionalone or more further first network monomers, oligomers or polymerscomprises a number average of 2 or more acrylate, methacrylate,itaconate, hydroxyl, epoxy, oxetane, vinyl ether, allyl ether, maleate,or fumarate groups. In an embodiment, the TPA-based polyester comprisesi) at least one acrylate or methacrylate group, and ii) at least oneepoxy group.

Throughout this patent application, when a polymerizable group isreferred to as “epoxy” or “epoxy group,” it is intended to encompass,without limitation, epoxy, oxirane, oxiranyl, glycidyl, orcycloaliphatic epoxy groups.

Further optional components are particulate fillers that may or may notbe able to (co)polymerize with the first network-forming component.

TPA-Based Polyester Component

The composition for forming a three-dimensional object comprises aTPA-based polyester. The TPA-based polyester comprises a backbone and anumber average of at least 2 polymerizable groups per molecule. Thebackbone comprises the reaction product of a terephthalic acid (TPA) anda polyol.

The backbone comprises a polyester formed from the polycondensationproduct of terephthalic acid and a polyol. A polyol is an alcohol havingtwo or more hydroxyl groups. In an embodiment, the polyol is a diol, atriol, or a tetraol. In an embodiment, the polyol is a pentaol or higherorder polyol. In an embodiment, the polyol is a diol. The TPA-basedpolyester may comprise just a single type of polyol and TPA, but mayalso comprise more than one type of polyol, such as two, three, four,five, or six different polyols, and TPA. In an embodiment the TPA-basedpolyester is linear. In an embodiment, the TPA-based polyester isbranched or dendritic.

In an embodiment, the polyol is an aliphatic or cylcoaliphatic polyol.In an embodiment, the polyol is an aromatic polyol. In an embodiment,the polyol has at least 2, at least 3, at least 4, at least 5, or atleast 6 hydroxyl groups. In an embodiment, the polyol has at most 2, atmost 3, at most 4, at most 5, at most 6, at most 8, or at most 10hydroxyl groups. In an embodiment, the polyol is linear. In anembodiment, the polyol is branched.

The polyol is selected such that the glass transition temperature (Tg)of the TPA-based polyester is 40° C. or more. In an embodiment, theTPA-based polyester has a Tg of at least 40° C., at least 45° C., atleast 50° C., at least 55° C., at least 60° C., at least 65° C., or atleast 70° C. In an embodiment, the Tg of the TPA-based polyester is 150°C. or less, 125° C. or less, or 120° C. or less.

In an embodiment, the polyol comprises a polyalkylene polyol or apolyalkylene oxide polyol. In an embodiment, the polyol comprises apolyethylene glycol, a polypropylene glycol, a polytetramethylene oxide(PTMO) polyol, a random or block polypropylene oxide-polyethylene oxidecopolymer polyol, a random or block polytetramethyleneoxide-polyethylene oxide copolymer polyol, a polycarbonate polyol, ahydroxyl-terminated silicone, a hydroxyalkyl-terminated silicone, arandom or block silicone-polyethyleneoxide copolymer polyol, apolybutadiene polyol, a polyisobutylene polyol, a polybutylene oxidepolyol, or a mixture thereof.

In an embodiment, the polyol comprises 1,4-butanediol, 1,2-propyleneglycol, 1,3-propylene glycol, dipropylene glycol, tripropylene glycol,ethylene glycol, diethylene glycol, triethylene glycol, trimethyleneglycol, tetramethylene glycol, pentamethylene glycol, hexamethyleneglycol, octamethylene glycol, decamethylene glycol, neopentyl glycol,1,6-hexanediol, hydrogenated bisphenol-A, ethoxylated bisphenol A,propoxylated bisphenol A, glycerol, 1,2,6-Hexanetriol,1,1,1-Tris(hydroxymethyl)propane, pentane-1,2,3-triol,propane-1,1,1-triol, 1,2-cyclohexanediol, 1,4-cyclohexanediol,1,1-cyclohexanedimethylol, cyclohexane-1,2,4-triol,cyclopropane-1,2,3-triol, benzenetriol, pentane-1,1,5,5-tetraol,hexane-1,2,5,6-tetraol, 1,2,4,5-tetrahydroxybenzene,butane-1,2,3,4-tetraol, [1,1′-biphenyl]-3,3′,5,5′-tetraol,trimethylolpropane, pentaerythritol, 1,4-cyclohexane dimethanol,phenyldiethanolamine, or a mixture thereof.

In an embodiment, the TPA-based polyester comprises a further polyacidother than TPA. In an embodiment, the further polyacid is an aliphaticpolyacid or an aromatic polyacid. In an embodiment, the further polyacidcomprises a dicarboxylic acid represented by the general formulaHOOC—Z—COOH wherein Z is aliphatic compound contains at least 2 carbonatoms. Such dicarboxylic acids include adipic acid, sebacic acid,phthalic acid, isophthalic acid, octadecanedioic acid, pimelic acid,suberic acid, azelaic acid, brassilic acid, dodecanedioic acid, glutaricacid, maleic acid, fumaric acid, 6-naphthalenedicarboxylic acid,4,4′-oxybisbenzoic acid, 3,6-dichlorophthalic acid, tetrachlorophthalicacid, tetrahydrophthalic acid, hexahydroterephthalic acid,hexachloroendomethylenetetrahydrophthalic acid,endomethylenetetrahydrophthalic acid, decanedicarboxylic acid, succinicacid, and trimellitic acid. In an embodiment, the further polyacidcomprises phthalic acid or isophthalic acid.

In an embodiment, at least 20 mol %, at least 30 mol %, at least 40 mol%, at least 50 mol %, at least 60 mol %, at least 70 mol %, at least 75mol %, at least 80 mol %, at least 85 mol %, at least 90 mol %, at least95 mol %, at least 98 mol %, or 100 mol % of the backbone of theTPA-based polyester comprises the reaction product of a polyacid and apolyol. In an embodiment, at most 100 mol %, at most 98 mol %, at most95 mol %, at most 90 mol %, at most 80 mol %, at most 70 mol %, or atmost 60 mol % of the backbone of the TPA-based polyester comprises thereaction product of a polyacid and a polyol.

In an embodiment, at least 20 mol %, at least 30 mol %, at least 40 mol%, at least 50 mol %, at least 60 mol %, at least 70 mol %, at least 75mol %, at least 80 mol %, at least 85 mol %, at least 90 mol %, at least95 mol %, at least 98 mol %, or 100 mol % of the backbone of theTPA-based polyester comprises the reaction product of TPA and a polyol.In an embodiment, at most 100 mol %, at most 98 mol %, at most 95 mol %,at most 90 mol %, at most 80 mol %, at most 70 mol %, or at most 60 mol% of the backbone of the TPA-based polyester comprises the reactionproduct of TPA and a polyol.

The TPA-based polyester comprises polymerizable groups that comprise anacrylate, methacrylate, epoxy, oxetane, hydroxyl, itaconate, vinylether, allyl ether, maleate, or fumarate. In an embodiment, thepolymerizable groups comprise acrylate, methacrylate, epoxy, oxetane, oritaconate. In an embodiment the polymerizable groups comprise acrylate,methacrylate, epoxy, or oxetane. In an embodiment, the polymerizablegroups comprise acrylate or methacrylate. In an embodiment, thepolymerizable groups comprise methacrylate. The polymerizable groups canbe formed by, for example, reacting a hydroxyl functional monomercomprising the desired polymerizable group with a carboxylic acidfunctional polymer comprising a TPA/polyol backbone. Another possibleway of forming the polymerizable groups is to react an OH group on thepolymer with a di or higher order isocyanate, and then reacting ahydroxyl functional monomer comprising the desired polymerizable groupwith the isocyanate group on the polymer. For example, the hydroxylfunctional monomer may be hydroxyethyl methacrylate.

In an embodiment, the polymerizable groups comprise endgroups. Anendgroup is a group present at the terminus of a polymer. In anembodiment, the polymerizable groups are endgroups and there are nopolymerizable groups that are not endgroups in the TPA-based polyester.

In an embodiment, the TPA-based polyester comprises a number average of2.0, at least 2.1, at least 2.2, at least 2.3, at least 2.4, at least2.5, at least 2.6, or at least 2.7 polymerizable groups per molecule. Inan embodiment, the TPA-based polyester comprises a number average of atmost 10, at most 9, at most 8, at most 7, at most 6, at most 5, at most4.5, at most 4, at most 3.5, or at most 3 polymerizable groups permolecule. In an embodiment, the TPA-based polyester comprises from 2.3-3polymerizable groups. Generally, as the functionality of the TPA-basedpolyester increases, the amount of the TPA-based polyester in thecomposition may decrease.

In an embodiment, the TPA-based polyester has a number average molecularweight of at least 800 g/mol, at least 900 g/mol, at least 1000 g/mol,at least 1100 g/mol, at least 1200 g/mol, at least 1300 g/mol, at least1400 g/mol, or at least 1500 g/mol. In an embodiment, the TPA-basedpolyester has a number average molecular weight of at most 10,000 g/mol,at most 9,000 g/mol, at most 8,000 g/mol, at most 7000 g/mol, at most6,000 g/mol, at most 5,000 g/mol, at most 4,000 g/mol, or at most 3,000g/mol.

In an embodiment, the TPA-based polyester has a number average of from 2to 3 polymerizable groups, and the amount, number average molecularweight, and number average of polymerizable groups of the TPA-basedpolyester in the composition satisfies the following equation to tunethe network density of the cured network:

${X\mspace{11mu} {MPa}} \leq {3*R*T*\left\lbrack {{\left( {3 - f} \right)*\left( \frac{\rho*w_{polyester}}{M_{polyester}} \right)} + {\left( {f - 2} \right)*3*\left( \frac{\rho*w_{polyester}}{M_{polyester}} \right)}} \right\rbrack} \leq {Y\mspace{11mu} {MPa}}$

wherein R is the gas constant 8.314 cm³ MPa K⁻¹ mol⁻¹, T is 423.15 K, fis the number average of polymerizable groups of the TPA-basedpolyester, ρ is the density of the TPA-based polyester in g/cm³,M_(polyester) is the number average molecular weight of the TPA-basedpolyester in g/mol, and w_(polyester) is the weight fraction of theTPA-based polyester in the first network-forming component. In anembodiment, X is 3, 5, 7, 10, 15, or 20. In an embodiment, Y is 50, 45,or 40. In an embodiment, the TPA-based polyester has a number average offrom 2 to 3 endgroups, and the amount, number average molecular weight,and number average of endgroups of the TPA-based polyester in thecomposition satisfies the above equation, and f is the number average ofendgroups of the TPA-based polyester.

It is possible that the TPA-based polyester achieves a number average offrom 2 to 3 polymerizable groups per molecule by a blend of TPA-basedpolyesters having different functionalities. For example, using 70 mol %of a TPA-based polyester having a number average of 2.3 polymerizablegroups per molecule and 30 mol % of a TPA-based polyester having anumber average of 4.0 polymerizable groups per molecule, is considered aTPA-based polyester having a number average of 2.8 polymerizable groupsper molecule. In this example, fin the above equation would be 2.8 andM_(polyester) is calculated based on the mol % of each TPA-basedpolyester.

In an embodiment, the TPA-based polyester is present in an amount of atleast 5 wt %, at least 10 wt %, at least 15 wt %, at least 19.95 wt %,at least 20 wt %, at least 25 wt %, at least 30 wt %, at least 40 wt %,at least 50 wt %, at least 60 wt %, at least 70 wt %, or at least 80 wt%, based on the total weight of the composition. In an embodiment, theTPA-based polyester is present in an amount of at most 80 wt %, at most78 wt %, at most 75 wt %, at most 70 wt %, at most 60 wt %, at most 50wt %, at most 40 wt %, at most 30 wt %, or at most 20 wt %, based on thetotal weight of the composition.

In an embodiment, the TPA-based polyester is present in an amount of atleast 5 wt %, at least 10 wt %, at least 15 wt %, at least 19.95 wt %,at least 20 wt %, at least 25 wt %, at least 30 wt %, at least 40 wt %,at least 50 wt %, at least 60 wt %, at least 70 wt %, or at least 80 wt%, based on the total weight of the composition excluding any solvent.In an embodiment, the TPA-based polyester is present in an amount of atmost 80 wt %, at most 78 wt %, at most 75 wt %, at most 70 wt %, at most60 wt %, at most 50 wt %, at most 40 wt %, at most 30 wt %, or at most20 wt %, based on the total weight of the composition excluding anysolvent.

In an embodiment, the TPA-based polyester is present in an amount of19.95 wt %, at least 20 wt %, at least 25 wt %, at least 30 wt %, atleast 40 wt %, at least 50 wt %, at least 60 wt %, at least 70 wt %, orat least 80 wt %, based on the total weight of the first network-formingcomponent. In an embodiment, the TPA-based polyester is present in anamount of at most 80 wt %, at most 78 wt %, at most 75 wt %, at most 70wt %, at most 60 wt %, at most 50 wt %, at most 40 wt %, at most 30 wt%, or at most 20 wt %, based on the total weight of the firstnetwork-forming component.

In an embodiment, the TPA-based polyester is amorphous. In anembodiment, the TPA-based polyester comprises a blend of amorphous andsemi-crystalline TPA-based polyesters. In an embodiment, the TPA-basedpolyester comprises a blend of amorphous, semi-crystalline, andcrystalline TPA-based polyesters.

First Network Monomer and First Network Initiator

In addition to the TPA-based polyester, the composition for forming athree-dimensional object via an additive fabrication process comprisesone or more first network monomers and a first network initiator.Depending on the polymerizable group(s) of the TPA-based polyester, thefirst network monomer and optional one or more further first networkmonomers, oligomers, or polymers may be free radically polymerizablecompounds or cationically polymerizable compounds, and the first networkinitiator may be a free-radical initiator or a cationic initiator. In anembodiment, the TPA-based polyester comprises a polymerizable groupcomprising acrylate, methacrylate, itaconate, allyl ether, maleate, orfumarate and the first network monomer and optional one or more furtherfirst network monomers, oligomers, or polymers are free radicallypolymerizable compounds and the first network initiator is afree-radical initiator. In an embodiment, the TPA-based polyestercomprises a polymerizable group comprising hydroxyl, epoxy, or oxetaneand the first network monomer and optional one or more further firstnetwork monomers, oligomers, or polymers are cationically polymerizablecompounds and the first network initiator is a cationic initiator.

In an embodiment, the TPA-based polyester comprises a number average ofat least 2 acrylate, methacrylate, itaconate, allyl ether, or fumarategroups per molecule, the one or more first network monomers comprise anacrylate, methacrylate, itaconate, vinyl ether, allyl ether, maleate, orfumarate group and the optional one or more further first networkmonomers, oligomers or polymers comprises a number average of 2 or moreacrylate, methacrylate, itaconate, vinyl ether, allyl ether, maleate, orfumarate groups. In an embodiment, the TPA-based polyester comprises anumber average of at least 2 hydroxyl, epoxy, or oxetane groups permolecule, the one or more first network monomers comprise a hydroxyl,epoxy, oxetane, or vinyl ether group and the optional one or morefurther first network monomers, oligomers or polymers comprises a numberaverage of 2 or more hydroxyl, epoxy, oxetane, or vinyl ether groups. Inan embodiment, the TPA-based polyester comprises a number average of atleast 2 vinyl ether groups per molecule, the one or more first networkmonomers comprise an acrylate, methacrylate, itaconate, hydroxyl, epoxy,oxetane, vinyl ether, allyl ether, maleate, or fumarate group and theoptional one or more further first network monomers, oligomers orpolymers comprises a number average of 2 or more acrylate, methacrylate,itaconate, hydroxyl, epoxy, oxetane, vinyl ether, allyl ether, maleate,or fumarate groups.

The polymerizable groups of the first network monomer are able to(co)polymerize with the polymerizable groups of the TPA-based polyester.The first network monomer has a number average of 0.95 to 1.1polymerizable groups. In an embodiment the first network monomer has anumber average of 0.95 polymerizable groups or more, 0.97 polymerizablegroups or more, or 0.99 polymerizable groups or more. In an embodimentthe first network monomer has a number average of 1.1 polymerizablegroups or less, 1.08 polymerizable groups or less, 1.06 polymerizablegroups or less, 1.04 polymerizable groups or less, or 1.02 polymerizablegroups or less. In an embodiment, the first network monomer has a numberaverage of 1.0 polymerizable groups.

A linear polymer formed from the one or more first network monomers hasa Tg of 40° C. or more. In an embodiment, a linear polymer formed fromthe one or more first network monomers has a Tg of 50° C. or more, 60°C. or more, 65° C. or more, 70° C. or more, 75° C. or more, 80° C. ormore, 85° C. or more, 90° C. or more, 95° C. or more, or 100° C. ormore. In an embodiment, a linear polymer formed from the one or morefirst network monomers has a Tg of 150° C. or less, 130° C. or less,125° C. or less, or 120° C. or less. It is possible that multiple firstnetwork monomers with different molecular formulas are present in theone or more first network monomers, some with a Tg of above the claimedamount and some with a Tg of below the claimed amount. A linear polymeris formed from all of the first network monomers together and the Tg ofthe linear polymer is measured to determine if the Tg is within theclaimed range.

In an embodiment, the one or more first network monomers has a molecularweight of 800 g/mol or less, 700 g/mol or less, 600 g/mol or less, 500g/mol or less, 400 g/mol or less, 350 g/mol or less, 300 g/mol or less,250 g/mol or less, or 200 g/mol or less. In an embodiment the one ormore first network monomers has a molecular weight of 100 g/mol or more,or 150 g/mol or more.

In an embodiment, the TPA-based polyester comprises a polymerizablegroup comprising acrylate, methacrylate, itaconate, vinyl ether, allylether, maleate, or fumarate and the first network monomer comprisesmethyl (meth)acrylate, hydroxy ethyl (meth)acrylate, ethyl(meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate,isobutyl (meth)acrylate, t-butyl (meth)acrylate, hydroxy propyl(meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl(meth)acrylate, isobornyl (meth)acrylate, isobutyl (meth)acrylate,acryloyl morpholine, dimethyl itaconate, N-vinyl pyrollidone, N-vinylcaprolactam, N-vinyl imidazole, or N-methyl-N-vinylacetamide. In anembodiment, the TPA-based polyester comprises a polymerizable groupcomprising acrylate, methacrylate, itaconate, vinyl ether, allyl ether,maleate, or fumarate and the first network monomer comprises cyclohexylvinyl ether, 1,4,-cyclohexanedimethanol mono vinyl ether, tert-Butylvinyl ether, phenyl vinyl ether, allyl phenyl ether, dimethyl maleate,diethyl maleate, dimethyl fumarate, or diethyl fumarate.

In an embodiment, the TPA-based polyester comprises a polymerizablegroup comprising hydroxyl, epoxy, oxetane, or vinyl ether and the one ormore first network monomers comprise cyclohexene oxide, tert-butylglycidyl ether, 4-chlorophenyl glycidyl ether, cyclopenteneoxide,exo-2,3-Epoxynorbornane, 1,2-Epoxy-3-phenoxypropane,(2,3-Epoxypropyl)benzene, N-(2,3-Epoxypropyl)phthalimide,exo-3,6-Epoxy-1,2,3,6-tetrahydrophthalic anhydride,3,4-Epoxytetrahydrothiophene-1,1-dioxide, Furfuryl glycidyl ether,glycidyl 4-methoxyphenyl ether, glycidyl 2-methylphenyl ether,isophorone oxide, α-Pinene oxide, cis-stilbene oxide, styrene oxide,Methyl,Methyl 7-oxabicyclo[4.1.0]heptane-3-carboxylate, 2-Ethylhexyl7-oxabicyclo(4.1.0)heptane-3-carboxylatecarboxylate,3-ethyl-3-hydroxymethyloxetane,3-ethyl-3-(3-hydroxypropyl)oxymethyloxetane,3-ethyl-3-(4-hydroxybutyl)oxymethyloxetane, cyclohexyl vinyl ether,1,4,-cyclohexanedimethanol mono vinyl ether, tert-Butyl vinyl ether, orphenyl vinyl ether.

In an embodiment, the one or more first network monomers are present inan amount of at least 10 wt %, at least 15 wt %, at least 19.95 wt %, atleast 20 wt %, at least 25 wt %, at least 30 wt %, at least 40 wt %, atleast 50 wt %, at least 60 wt %, at least 70 wt %, or at least 80 wt %,based on the total weight of the composition. In an embodiment, the oneor more first network monomers are present in an amount of at most 80 wt%, at most 78 wt %, at most 75 wt %, at most 70 wt %, at most 60 wt %,at most 50 wt %, at most 40 wt %, at most 30 wt %, or at most 20 wt %,based on the total weight of the composition.

In an embodiment, the one or more first network monomers are present inan amount of at least 10 wt %, at least 15 wt %, at least 19.95 wt %, atleast 20 wt %, at least 25 wt %, at least 30 wt %, at least 40 wt %, atleast 50 wt %, at least 60 wt %, at least 70 wt %, or at least 80 wt %,based on the total weight of the composition excluding any solvent. Inan embodiment, the one or more first network monomers are present in anamount of at most 80 wt %, at most 78 wt %, at most 75 wt %, at most 70wt %, at most 60 wt %, at most 50 wt %, at most 40 wt %, at most 30 wt%, or at most 20 wt %, based on the total weight of the compositionexcluding any solvent.

In an embodiment, the one or more first network monomers are present inan amount of at least 19.95 wt %, at least 20 wt %, at least 25 wt %, atleast 30 wt %, at least 40 wt %, at least 50 wt %, at least 60 wt %, atleast 70 wt %, or at least 80 wt %, based on the total weight of thefirst network-forming component. In an embodiment, the one or more firstnetwork monomers are present in an amount of at most 80 wt %, at most 78wt %, at most 75 wt %, at most 70 wt %, at most 60 wt %, at most 50 wt%, at most 40 wt %, at most 30 wt %, or at most 20 wt %, based on thetotal weight of the first network-forming component.

The first network initiator serves to initiate polymerization of theTPA-based polyester, the one or more first network monomers, optionally,the one or more further first network monomers, oligomers, or polymers,and, optionally, the particulate filler comprising a polymerizable groupthat is able to (co)polymerize with the polymerizable groups of theTPA-based polyester. In an embodiment, the one or more first networkinitiators comprise a photo-initiator or a thermal initiator. In anembodiment, the one or more first network initiators comprise aphoto-initiator that initiates polymerization in response to UV light,visible light, or both UV light and visible light. In an embodiment, theone or more first network initiators comprise a photo-initiator thatinitiates polymerization at a wavelength of from 300 to 470 nm. In anembodiment, the one or more first network initiators comprise aphoto-initiator that initiates polymerization at a wavelength of from300 to 395 nm. In an embodiment, the one or more first networkinitiators comprise a photo-initiator and a thermal initiator.

In an embodiment, the one or more first network initiators comprise athermal initiator. The thermal initiator may be used to further cure thecomposition during a thermal post-treatment of an article formed fromthe composition.

In an embodiment, the one or more first network initiators are presentin an amount of at least 0.01 wt %, at least 0.05 wt %, at least 0.1 wt%, at least 0.2 wt %, at least 0.3 wt %, at least 0.4 wt %, at least 0.5wt %, at least 1.0 wt %, at least 1.5 wt %, at least 2 wt %, or at least2.5 wt %, based on the total weight of the composition. In anembodiment, the one or more first network monomers are present in anamount of at most 10 wt %, at most 8 wt %, at most 7 wt %, at most 6 wt%, at most 5 wt %, or at most 4 wt %, based on the total weight of thecomposition.

In an embodiment, the one or more first network initiators are presentin an amount of at least 0.01 wt %, at least 0.05 wt %, at least 0.1 wt%, at least 0.2 wt %, at least 0.3 wt %, at least 0.4 wt %, at least 0.5wt %, at least 1.0 wt %, at least 1.5 wt %, at least 2 wt %, or at least2.5 wt %, based on the total weight of the composition excluding anysolvent. In an embodiment, the one or more first network monomers arepresent in an amount of at most 10 wt %, at most 8 wt %, at most 7 wt %,at most 6 wt %, at most 5 wt %, or at most 4 wt %, based on the totalweight of the composition excluding any solvent.

In an embodiment, the one or more first network initiators are presentin an amount of at least 0.01 wt %, at least 0.05 wt %, at least 0.1 wt%, at least 0.2 wt %, at least 0.3 wt %, at least 0.4 wt %, at least 0.5wt %, at least 1.0 wt %, at least 1.5 wt %, at least 2 wt %, or at least2.5 wt %, based on the total weight of the first network-formingcomponent. In an embodiment, the one or more first network initiatorsare present in an amount of at most 10 wt %, at most 8 wt %, at most 7wt %, at most 6 wt %, at most 5 wt %, or at most 4 wt %, based on thetotal weight of the first network-forming component.

Further First Network Monomer, Oligomer, or Polymer

Optionally, the composition comprises one or more further first networkmonomers, oligomers, or polymers having a number average of 2 or morepolymerizable groups that are able to (co)polymerize with thepolymerizable groups of the TPA-based polyester or the one or morefirst-network monomers.

In an embodiment, the one or more further first network monomers,oligomers, or polymers is present in an amount of at most 15 wt %, atmost 12 wt %, at most 10 wt %, at most 8 wt %, at most 6 wt %, at most 5wt %, at most 4 wt %, at most 3 wt %, or at most 2 wt %, based on thetotal weight of the composition. In an embodiment, the one or morefurther first network monomers, oligomers, or polymers is present in anamount of at least 0.5 wt %, at least 1 wt %, at least 1.5 wt %, atleast 2 wt %, at least 2.5 wt %, at least 4 wt %, or at least 5 wt %,based on the total weight of the composition.

In an embodiment, the one or more further first network monomers,oligomers, or polymers is present in an amount of at most 15 wt %, atmost 12 wt %, at most 10 wt %, at most 8 wt %, at most 6 wt %, at most 5wt %, at most 4 wt %, at most 3 wt %, or at most 2 wt %, based on thetotal weight of the composition excluding any solvent. In an embodiment,the one or more further first network monomers, oligomers, or polymersis present in an amount of at least 0.5 wt %, at least 1 wt %, at least1.5 wt %, at least 2 wt %, at least 2.5 wt %, at least 4 wt %, or atleast 5 wt %, based on the total weight of the composition excluding anysolvent.

In an embodiment, the one or more further first network monomers,oligomers, or polymers is present in an amount of at most 15 wt %, atmost 12 wt %, at most 10 wt %, at most 8 wt %, at most 6 wt %, at most 5wt %, at most 4 wt %, at most 3 wt %, or at most 2 wt %, based on thetotal weight of the first network-forming component. In an embodiment,the one or more further first network monomers, oligomers, or polymersis present in an amount of at least 0.5 wt %, at least 1 wt %, at least1.5 wt %, at least 2 wt %, at least 2.5 wt %, at least 4 wt %, or atleast 5 wt %, based on the total weight of the first network-formingcomponent.

Optional Second Network-Forming Component

Optionally, the composition comprises a second network-formingcomponent. The second network-forming component comprises one or moresecond network compounds comprising polymerizable groups that do not(co)polymerize with the polymerizable groups of the TPA-based polyester,and a second network initiator for initiating the polymerization of theone or more second network compounds. In an embodiment, the TPA-basedpolyester comprises polymerizable groups comprising acrylate,methacrylate, or itaconate, and the one or more second network compoundscomprises polymerizable groups that comprise epoxy, oxetane, orhydroxyl.

In an embodiment, the second network-forming component is present in anamount of 5 wt % or more, 10 wt % or more, 15 wt % or more, 20 wt % ormore, 25 wt % or more, 30 wt % or more, 35 wt % or more, 40 wt % ormore, 50 wt % or more, 60 wt % or more, or 70 wt % or more, based on thetotal weight of the composition. In an embodiment the secondnetwork-forming component is present in an amount of 90 wt % or less, 80wt % or less, 70 wt % or less, 60 wt % or less, 50 wt % or less, 40 wt %or less, 30 wt % or less, or 20 wt % or less, based on the total weightof the composition. In an embodiment, the composition is devoid ofsecond network-forming component. In an embodiment, the composition issubstantially devoid of second network-forming component.

In an embodiment, the second network-forming component is present in anamount of 5 wt % or more, 10 wt % or more, 15 wt % or more, 20 wt % ormore, 25 wt % or more, 30 wt % or more, 35 wt % or more, 40 wt % ormore, 50 wt % or more, 60 wt % or more, or 70 wt % or more, based on thetotal weight of the composition, excluding the weight of any solvent. Inan embodiment the second network-forming component is present in anamount of 90 wt % or less, 80 wt % or less, 70 wt % or less, 60 wt % orless, 50 wt % or less, 40 wt % or less, 30 wt % or less, or 20 wt % orless, based on the total weight of the composition excluding anysolvent.

In an embodiment, the second network-forming component is present in anamount of 5 wt % or more, 10 wt % or more, 15 wt % or more, 20 wt % ormore, 25 wt % or more, 30 wt % or more, 35 wt % or more, 40 wt % ormore, 50 wt % or more, 60 wt % or more, or 70 wt % or more, based on thetotal weight of the composition excluding any solvent and any componentsthat do not comprise a polymerizable group. In an embodiment the secondnetwork-forming component is present in an amount of 90 wt % or less, 80wt % or less, 70 wt % or less, 60 wt % or less, 50 wt % or less, 40 wt %or less, 30 wt % or less, or 20 wt % or less, based on the total weightof the composition excluding any solvent and any components that do notcomprise a polymerizable group.

In an embodiment, the one or more second network compounds are presentin an amount of at least 5 wt %, at least 10 wt %, at least 15 wt %, atleast 19.95 wt %, at least 20 wt %, at least 25 wt %, at least 30 wt %,at least 40 wt %, at least 50 wt %, at least 60 wt %, at least 70 wt %,or at least 80 wt %, based on the total weight of the composition. In anembodiment, the one or more second network compounds are present in anamount of at most 80 wt %, at most 78 wt %, at most 75 wt %, at most 70wt %, at most 60 wt %, at most 50 wt %, at most 40 wt %, at most 30 wt%, or at most 20 wt %, based on the total weight of the composition.

In an embodiment, the one or more second network compounds are presentin an amount of at least 5 wt %, at least 10 wt %, at least 15 wt %, atleast 19.95 wt %, at least 20 wt %, at least 25 wt %, at least 30 wt %,at least 40 wt %, at least 50 wt %, at least 60 wt %, at least 70 wt %,or at least 80 wt %, based on the total weight of the compositionexcluding any solvent. In an embodiment, the one or more second networkcompounds are present in an amount of at most 80 wt %, at most 78 wt %,at most 75 wt %, at most 70 wt %, at most 60 wt %, at most 50 wt %, atmost 40 wt %, at most 30 wt %, or at most 20 wt %, based on the totalweight of the composition excluding any solvent.

In an embodiment, the one or more second network compounds are presentin an amount of at least 50 wt %, at least 60 wt %, at least 70 wt %, atleast 80 wt %, or at least 90 wt %, based on the total weight of thesecond network-forming component. In an embodiment, the one or moresecond network compounds are present in an amount of at most 99.9 wt %,at most 99.5 wt %, at most 99 wt %, at most 98 wt %, at most 97 wt %, atmost 96 wt %, at most 95 wt %, at most 90 wt %, or at most 80 wt %,based on the total weight of the second network-forming component.

In an embodiment, the second network initiator comprises aphoto-initiator or a thermal initiator. In an embodiment, the secondnetwork initiator comprises a photo-initiator that initiatespolymerization in response to UV light, visible light, or both UV lightand visible light. In an embodiment, the second network initiatorcomprises a photo-initiator and a thermal initiator.

In an embodiment, the second network initiator is present in an amountat least 0.01 wt %, at least 0.05 wt %, at least 0.1 wt %, at least 0.2wt %, at least 0.3 wt %, at least 0.4 wt %, at least 0.5 wt %, at least1.0 wt %, at least 1.5 wt %, at least 2 wt %, or at least 2.5 wt %,based on the total weight of the composition excluding any solvent. Inan embodiment, the second network initiator is present in an amount ofat most 10 wt %, at most 8 wt %, at most 7 wt %, at most 6 wt %, at most5 wt %, or at most 4 wt %, based on the total weight of the compositionexcluding any solvent.

In an embodiment, the second network initiator is present in an amountof at least 0.01 wt %, at least 0.05 wt %, at least 0.1 wt %, at least0.2 wt %, at least 0.3 wt %, at least 0.4 wt %, at least 0.5 wt %, atleast 1.0 wt %, at least 1.5 wt %, at least 2 wt %, or at least 2.5 wt%, based on the total weight of the second network-forming component. Inan embodiment, the second network initiator is present in an amount ofat most 10 wt %, at most 8 wt %, at most 7 wt %, at most 6 wt %, at most5 wt %, or at most 4 wt %, based on the total weight of the secondnetwork-forming component.

Various components comprising polymerizable groups may be present in thecomposition. Below, various free radically polymerizable compounds andcationically polymerizable compounds are described. Depending on thepolymerizable groups of the TPA-based polyester and the number averageof polymerizable groups of the compounds, these compounds may be firstnetwork monomers, further first network monomers, oligomers or polymers,or second network compounds comprising polymerizable groups.

Free Radically Polymerizable Compounds

In an embodiment, the first network-forming component or secondnetwork-forming component comprises at least one free radicallypolymerizable compound, that is, a component which undergoespolymerization initiated by free radicals. Free radically polymerizablecompounds are monomers, oligomers, and/or polymers; they aremonofunctional or polyfunctional materials, i.e., have 1, 2, 3, 4, 5, 6,7, 8, 9, 10, 20, 30, 40, 50, 100, or more functional groups that canpolymerize by free radical initiation, may contain aliphatic, aromatic,cycloaliphatic, arylaliphatic, each of which may comprise one or moreheteroatoms, or any combination thereof.

In accordance with an embodiment, the first network-forming component orsecond network-forming component comprises a component comprising atleast one polymerizable (meth)acrylate group. Examples of componentscomprising at least one polymerizable (meth)acrylate group includeacrylates and methacrylates such as isobornyl (meth)acrylate, bornyl(meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl(meth)acrylate, dicyclopentenyl (meth)acrylate, cyclohexyl(meth)acrylate, benzyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate,acryloyl morpholine, (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate,2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl(meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl(meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl(meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate,caprolactone acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate,heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate,2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate,isodecyl (meth)acrylate, tridecyl (meth)acrylate, undecyl(meth)acrylate, lauryl (meth)acrylate, tetradecyl (meth)acrylate,stearyl (meth)acrylate, isostearyl (meth)acrylate, tetrahydrofurfuryl(meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol(meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate,2-(2-ethoxyethoxy)ethyl acrylate, acetoacetoxy (meth)acrylate,polyethylene glycol mono(meth)acrylate, polypropylene glycolmono(meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethyl(meth)acrylate, methoxypolyethylene glycol (meth)acrylate,methoxypolypropylene glycol (meth)acrylate, diacetone (meth)acrylamide,beta-carboxyethyl (meth)acrylate, phthalic acid (meth)acrylate,dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate,butylcarbamylethyl (meth)acrylate, n-isopropyl (meth)acrylamidefluorinated (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate,2-(phenylthio)ethyl acrylate, and nonyl phenol acrylate.

Examples of components comprising more than one (meth)acrylate groupinclude those with (meth)acryloyl groups such as trimethylolpropanetri(meth)acrylate, pentaerythritol (meth)acrylate, ethylene glycoldi(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate,dicyclopentadiene dimethanol di(meth)acrylate,[2-1,1-dimethyl-2-[(1-oxoallyl)oxy]ethyl]-5-ethyl-1,3-dioxan-5-yl]methylacrylate;3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecanedi(meth)acrylate; dipentaerythritol monohydroxypenta(meth)acrylate,propoxylated trimethylolpropane tri(meth)acrylate, ethoxylatedtrimethylolpropane tri(meth)acrylate, propoxylated neopentyl glycoldi(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethyleneglycol di(meth)acrylate, polypropylene glycol di(meth)acrylate,1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate,neopentyl glycol di(meth)acrylate, polybutanediol di(meth)acrylate,tripropyleneglycol di(meth)acrylate, glycerol tri(meth)acrylate,phosphoric acid mono- and di(meth)acrylates, C₇-C₂₀ alkyldi(meth)acrylates, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate,tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, pentaerythritoltri(meth)acrylate, pentaerythritol tetra(meth)acrylate,dipentaerythritol hexa(meth)crylate, tricyclodecane diyl dimethyldi(meth)acrylate and alkoxylated versions (e.g., ethoxylated and/orpropoxylated) of any of the preceding monomers, and alsodi(meth)acrylate of a diol which is an ethylene oxide or propylene oxideadduct to bisphenol A, di(meth)acrylate of a diol which is an ethyleneoxide or propylene oxide adduct to hydrogenated bisphenol A, epoxy(meth)acrylate which is a (meth)acrylate adduct to bisphenol A ofdiglycidyl ether, diacrylate of polyoxyalkylated bisphenol A, andtriethylene glycol divinyl ether, and adducts of hydroxyethyl acrylate.

In accordance with an embodiment, the first network-forming component orsecond network-forming component comprises all methacrylate groups, allacrylate groups, or any combination of methacrylate and acrylate groups.

In an embodiment, the free radically polymerizable compound comprisesbisphenol A diglycidyl ether di(meth)acrylate, ethoxylated orpropoxylated bisphenol A or bisphenol F di(meth)acrylate,dicyclopentadiene dimethanol di(meth)acrylate,[2-[1,1-dimethyl-2-[(1-oxoallyl)oxy]ethyl]-5-ethyl-1,3-dioxan-5-yl]methylacrylate, di pentaerythritol monohydroxypenta(meth)acrylate,dipentaerythritol hexa(meth)crylate, propoxylated trimethylolpropanetri(meth)acrylate, or propoxylated neopentyl glycol di(meth)acrylate, orany combination thereof.

In an embodiment, the free radically polymerizable compound comprises anester formed from itaconic acid, citraconic acid, or mesaconic acid. Inan embodiment, the free radically polymerizable compound is dimethylitaconate.

In an embodiment, the free radically polymerizable compound comprises athiol-containing compound. In an embodiment, the free radicallypolymerizable compound comprises an aliphatic thiol, more preferably aprimary aliphatic thiol. In an embodiment, the free radicallypolymerizable compound comprises an aromatic thiol. In an embodiment,the thiol-containing compound comprises an aliphatic thiol and comprisesan α-mercapto acetate or β-mercapto propionate, or a derivative ormixture thereof. In an embodiment, the thiol-containing compoundcomprises dodecyl mercaptan or octyl mercaptan, In an embodiment, thefree radically polymerizable compound comprises a dithioester, athioether, a thione, a trithiocarbonate, such asdibenzyltrithiocarbonate, a dithiocarbamate, a xanthate, such asO-ethyl-S-(1-methoxycarbonyl)ethyl dithiocarbonate [RSC(═S)—OC₂H₅ whereR is —CH(CH₃)—C(═O)—OCH₃], or a mixture thereof.

Cationically Polymerizable Compounds

In an embodiment, the first network-forming component or secondnetwork-forming component comprises at least one cationicallypolymerizable compound, that is, a compound which undergoes cationicpolymerization. The cationically polymerizable compound may be selectedfrom the group consisting of cyclic ether compounds, cyclic acetalcompounds, cyclic thioethers compounds, spiro-orthoester compounds,cyclic lactone compounds, and vinyl ether compounds, and any combinationthereof. Of the cationically polymerizable groups that may be present inthe composition, cycloaliphatic epoxy and oxetane groups generally havethe fastest reactivity and are thus preferred for that reason.

Examples of cationically polymerizable compounds include cyclic ethercompounds such as epoxy compounds, oxetane compounds, cyclic lactonecompounds, cyclic acetal compounds, cyclic thioether compounds, spiroorthoester compounds, and vinylether compounds. Specific examples ofcationically polymerizable compounds include bisphenol A diglycidylether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether,brominated bisphenol A diglycidyl ether, brominated bisphenol Fdiglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolacresins, hydrogenated bisphenol A diglycidyl ether, hydrogenatedbisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether,3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate,2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)-cyclohexane-1,4-dioxane,bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene oxide,4-vinylepoxycyclohexane, vinylcyclohexene dioxide, limonene oxide,limonene dioxide, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate,3,4-epoxy-6-methylcyclohexyl-3′,4′-epoxy-6′-methylcyclohexanecarboxylate,ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylates, trimethylcaprolactone-modified3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylates,β-methyl-δ-valerolactone-modified3,4-epoxycyclohexcylmethyl-3′,4′-epoxycyclohexane carboxylates,methylenebis(3,4-epoxycyclohexane), bicyclohexyl-3,3′-epoxide,bis(3,4-epoxycyclohexyl) with a linkage of —O—, —S—, —SO—, —SO₂—,—C(CH₃)₂—, —CBr₂—, —C(CBr₃)₂—, —C(CF₃)₂—, —C(CCl₃)₂—, or —CH(C₆H₅)—,dicyclopentadiene diepoxide, di(3,4-epoxycyclohexylmethyl) ether ofethylene glycol, ethylenebis(3,4-epoxycyclohexanecarboxylate),epoxyhexahydrodioctylphthalate, epoxyhexahydro-di-2-ethylhexylphthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidylether, neopentylglycol diglycidyl ether, glycerol triglycidyl ether,trimethylolpropane triglycidyl ether, polyethylene glycol diglycidylether, polypropylene glycol diglycidyl ether, polyglycidyl ethers ofpolyether polyol obtained by the addition of one or more alkylene oxidesto aliphatic polyhydric alcohols such as ethylene glycol, propyleneglycol, and glycerol, diglycidyl esters of aliphatic long-chain dibasicacids, monoglycidyl ethers of aliphatic higher alcohols, monoglycidylethers of phenol, cresol, butyl phenol, or polyether alcohols obtainedby the addition of alkylene oxide to these compounds, glycidyl esters ofhigher fatty acids, epoxidated soybean oil, epoxybutylstearic acid,epoxyoctylstearic acid, epoxidated linseed oil, epoxidatedpolybutadiene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene,3-ethyl-3-hydroxymethyloxetane,3-ethyl-3-(3-hydroxypropyl)oxymethyloxetane,3-ethyl-3-(4-hydroxybutyl)oxymethyloxetane,3-ethyl-3-(5-hydroxypentyl)oxymethyloxetane,3-ethyl-3-phenoxymethyloxetane, bis((1-ethyl(3-oxetanyl))methyl)ether,3-ethyl-3-((2-ethylhexyloxy)methyl)oxetane,3-ethyl-((triethoxysilylpropoxymethyl)oxetane,3-(meth)-allyloxymethyl-3-ethyloxetane,(3-ethyl-3-oxetanylmethoxy)methyl benzene,4-fluoro-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene,4-methoxy-[1-(3-ethyl-3-oxetanylmethoxy)methyl]-benzene,[1-(3-ethyl-3-oxetanylmethoxy)ethyl]phenyl ether,isobutoxymethyl(3-ethyl-3-oxetanylmethyl)ether,2-ethylhexyl(3-ethyl-3-oxetanylmethyl)ether, ethyldiethyleneglycol(3-ethyl-3-oxetanylmethyl)ether, dicyclopentadiene(3-ethyl-3-oxetanylmethyl)ether,dicyclopentenyloxyethyl(3-ethyl-3-oxetanylmethyl)ether,dicyclopentenyl(3-ethyl-3-oxetanylmethyl)ether,tetrahydrofurfuryl(3-ethyl-3-oxetanylmethyl)ether,2-hydroxyethyl(3-ethyl-3-oxetanylmethyl)ether,2-hydroxypropyl(3-ethyl-3-oxetanylmethyl)ether, and any combinationthereof.

Examples of polyfunctional materials that are cationically polymerizableinclude dendritic polymers such as dendrimers, linear dendriticpolymers, dendrigraft polymers, hyperbranched polymers, star branchedpolymers, and hypergraft polymers with epoxy, oxetane, or hydroxylfunctional groups. The dendritic polymers may contain one type ofpolymerizable functional group or different types of polymerizablefunctional groups, for example, epoxy and oxetane functions.

In an embodiment, the cationically polymerizable compound comprises ahydroxyl functional component comprising at least one primary OH group.In an embodiment, the cationically polymerizable compound comprises ahydroxyl functional component comprising two primary OH groups.

In an embodiment, the cationically polymerizable compound comprises adiol of number average molecular weight less than about 500 g/mol. In anembodiment, the cationically polymerizable compound comprises a diol ofnumber average molecular weight less than about 400 g/mol. In anembodiment, the cationically polymerizable compound comprises ethyleneglycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol,1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol,1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol,triethyleneglycol, tetraethylene glycol, dipropylene glycol ortripropylene glycol. In an embodiment, the cationically polymerizablecompound comprises a polyol with three or more OH groups, such astrimethylolpropane, glycerol, or pentaerythritol.

In an embodiment, the cationically polymerizable component comprises analkoxylated polyol, such as ethoxylated or propoxylated versions of thepolyols in the previous paragraph. However, alkoxylated polyols may havethe effect of lowering the Tg of an article produced by polymerizing thecomposition, and should therefore be used with care. In an embodiment,the cationically polymerizable component comprises an alkoxylatedaromatic diol. In an embodiment, the cationically polymerizable compoundcomprises a bisphenol A with ethoxylations and/or propoxylations. Thisbisphenol A may for example contain in total between about 1 and about30 ethoxylations and/or propoxylations per hydroxyl group.

In an embodiment, the cationically polymerizable component comprisespoly(propylene glycol) or copolymers thereof, poly(ethylene glycol) orcopolymers thereof, poly(teramethylene oxide) or copolymers thereof,poly(butylene oxide) or copolymers thereof, hydroxyl-terminatedpoly(butadiene), poly(caprolactone) diols, poly(caprolactam)diolshydroxyl-terminated poly(acrylate), hydroxyl-terminated poly(ester),poly(carbonate) telechelic diols, poly(ether) telechelic diols,poly(urethane) telechelic diols, hydroxyl-terminated poly(dimethylsiloxane) and copolymers thereof.

Various types of initiators may be present in the composition. Below,various free radical initiators and cationic initiators are described.Depending on the polymerizable groups of the TPA-based polyester, theseinitiators may be first network initiators or second network initiators.

Polymerization may be initiated by any suitable way, depending on thenecessary initiation mechanism for the initiators. In an embodiment,polymerization is initiated via irradiation of the composition withlight or heat. Preferably, the polymerizable composition is polymerizedby applying UV or visible light. The radiation may be provided by alamp, laser, LED, or other light sources.

Free-Radical Polymerization Initiator

In the case that the first network-forming component or secondnetwork-forming component comprises a free radically polymerizablecompound, the respective first network-forming component or secondnetwork-forming component also comprises a free-radical polymerizationinitiator. Preferred examples of free-radical polymerization initiatorsare thermal initiators and photo-initiators. Preferably, thefree-radical polymerization initiator comprises a free-radicalphoto-initiator.

In accordance with an embodiment, the first network-forming component orsecond network-forming component comprises at least one free-radicalphoto-initiator. In an embodiment, the free-radical photo-initiator isselected from the group consisting of benzoylphosphine oxides, arylketones, benzophenones, hydroxylated ketones, I-hydroxyphenyl ketones,ketals, metallocenes, and any combination thereof.

In an embodiment, the first network-forming component or secondnetwork-forming component includes at least one free-radicalphoto-initiator selected from the group consisting of2,4,6-trimethylbenzoyl diphenylphosphine oxide and2,4,6-trimethylbenzoyl phenyl, ethoxy phosphine oxide,bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1,2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl) phenyl]-1-butanone,2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one,4-benzoyl-4′-methyl diphenyl sulphide, 4,4′-bis(diethylamino)benzophenone, and 4,4′-bis(N,N′-dimethylamino) benzophenone (Michler'sketone), benzophenone, 4-methyl benzophenone, 2,4,6-trimethylbenzophenone, dimethoxybenzophenone, I-hydroxycyclohexyl phenyl ketone,phenyl (1-hydroxyisopropyl)ketone, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone,4-isopropylphenyl(1-hydroxyisopropyl)ketone,oligo-[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] propanone],camphorquinone, 4,4′-bis(diethylamino) benzophenone, benzil dimethylketal, bis(eta 5-2-4-cyclopentadien-1-yl)bis[2,6-difluoro-3-(1H-pyrrol-1-yl) phenyl] titanium, and anycombination thereof.

Further free-radical photo-initiators include: benzoylphosphine oxides,such as, for example, 2,4,6-trimethylbenzoyl diphenylphosphine oxide(Lucirin TPO from BASF) and 2,4,6-trimethylbenzoyl phenyl, ethoxyphosphine oxide (Lucirin TPO-L from BASF),bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide (Irgacure 819 or BAPOfrom Ciba), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1(Irgacure 907 from Ciba),2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl) phenyl]-1-butanone(Irgacure 369 from Ciba),2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one(Irgacure 379 from Ciba), 4-benzoyl-4′-methyl diphenyl sulphide(Chivacure BMS from Chitec), 4,4′-bis(diethylamino) benzophenone(Chivacure EMK from Chitec), 4,4′-bis(N,N′-dimethylamino) benzophenone(Michler's ketone), camphorquinone, 4,4′-bis(diethylamino) benzophenone(Chivacure EMK from Chitec), 4,4′-bis(N,N′-dimethylamino) benzophenone(Michler's ketone), bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide(Irgacure 819 or BAPO from Ciba), and metallocenes such as bis (eta5-2-4-cyclopentadien-1-yl) bis [2,6-difluoro-3-(1H-pyrrol-1-yl) phenyl]titanium (Irgacure 784 from Ciba), or a mixture thereof.

Examples of thermal free-radical polymerization initiators include, butare not limited to, azo compounds such as, for example, azoisobutyronitrile (AlBN), 1,1′-azobis(cyclohexanenitrile),1,1′-azobis(2,4,4-trimethylpentane), C—C labile compounds, such asbenzopinacole, peroxides, and mixtures thereof.

In an embodiment, the free-radical polymerization comprises a peroxide.Possibly suitable peroxides include organic and inorganic peroxides. Inan embodiment, the thermal initiator is soluble in the composition.

Examples of peroxides include for example, percarbonates (of the formula—OC(O)O—), peroxyesters (of the formula —C(O)OO—), diacylperoxides, alsoknown as peranhydride (of the formula —C(O)OOC(O)—), dialkylperoxides orperethers (of the formula —OO—), hydroperoxides (of the formula —OOH),etc. The peroxides may also be oligomeric or polymeric in nature.

The thermal free-radical polymerization initiator may for examplecomprise a percarbonate, a perester or a peranhydride. Peranhydrides arefor example benzoylperoxide (BPO) and lauroyl peroxide (commerciallyavailable as Laurox™) Peresters are for instance t-butyl per benzoateand 2-ethylhexyl perlaurate. Percarbonates are for exampledi-t-butylpercarbonate and di-2-ethylhexylpercarbonate ormonopercarbonates.

In an embodiment, the thermal free-radical polymerization initiator isan organic peroxide. Examples of organic peroxides are: tertiary alkylhydroperoxides (such as, for instance, t-butyl hydroperoxide), otherhydroperoxides (such as, for instance, cumene hydroperoxide), a ketoneperoxide (perketones, being an addition product of hydrogen peroxide anda ketone, such as, for instance, methyl ethyl ketone peroxide, methylisobutylketone peroxide and acetylacetone peroxide), peroxyesters orperacids (such as, for instance, t-butyl peresters, benzoyl peroxide,peracetates and perbenzoates, lauroyl peroxide, including(di)peroxyesters, perethers (such as, for instance, peroxy diethylether).

In an embodiment, the thermal free-radical polymerization initiatorcomprises a peranhydride, for example benzoyl peroxide or lauroylperoxide, peroxydicarbonate, for exampledi(4-t-butylcyclohexyl)-peroxydicarbonate, dicetyl peroxydicarbonate, ordimyristylperoxydicarbonate.

Cationic Polymerization Initiator

In the case that the first network-forming component or secondnetwork-forming component comprises a free radically polymerizablecompound, the respective first network-forming component or secondnetwork-forming component also comprises a cationic polymerizationinitiator. Preferred examples of cationic polymerization initiators arethermal initiators and photo-initiators. Preferably, the cationicpolymerization initiator is a catonic photo-initiator. The cationicphoto-initiator initiates cationic ring-opening polymerization uponirradiation with light.

In an embodiment, the cationic photo-initiator comprises a cation ofonium salts, halonium salts, iodosyl salts, selenium salts, sulfoniumsalts, sulfoxonium salts, diazonium salts, metallocene salts,isoquinolinium salts, phosphonium salts, arsonium salts, tropyliumsalts, dialkylphenacylsulfonium salts, thiopyrilium salts, diaryliodonium salts, triaryl sulfonium salts, ferrocenes,di(cyclopentadienyliron)arene salt compounds, and pyridinium salts, orany combination thereof.

In another embodiment, the cation of the cationic photo-initiator isselected from the group consisting of aromatic diazonium salts, aromaticsulfonium salts, aromatic iodonium salts, metallocene based compounds,aromatic phosphonium salts, polymeric sulfonium salts,naphthyl-sulfonium salts, and any combination thereof. In an embodiment,the cationic photo-initiator is selected from the group consisting oftriarylsulfonium salts, diaryliodonium salts, and metallocene basedcompounds, and any combination thereof.

In an embodiment, the cationic photo-initiator has an anion selectedfrom the group consisting of BF₄ ⁻, AsF6⁻, SbF₆ ⁻, PF₆ ⁻, [B(CF₃)₄]⁻,B(C₆F₅)₄ ⁻, B[C₆H₃-3,5(CF₃)₂]₄ ⁻, B(C₆H₄CF₃)₄ ⁻, B(C₆H₃F₂)₄ ⁻,B[C₆F₄-4(CF₃)]₄ ⁻, Ga(C₆F₅)₄ ⁻, [(C₆F₅)₃B—C₃H₃N₂—B(C₆F₅)₃]⁻,[(C₆F₅)₃B—NH₂—B(C₆P₅)₃]⁻, tetrakis(3,5-difluoro-4-alkyloxyphenyl)borate,tetrakis(2,3,5,6-tetrafluoro-4-alkyloxyphenyl)borate,perfluoroalkylsulfonates, tris[(perfluoroalkyl)sulfonyl]methides,bis[(perfluoroalkyl)sulfonyl]imides, perfluoroalkylphosphates,tris(perfluoroalkyl)trifluorophosphates,bis(perfluoroalkyl)tetrafluorophosphates,tris(pentafluoroethyl)trifluorophosphates, and (CH₆B₁₁Br₆)⁻,(CH₆B₁₁Cl₆)⁻ and other halogenated carborane anions.

In an embodiment, the cationic photo-initiator has a cation selectedfrom the group consisting of aromatic sulfonium salts, aromatic iodoniumsalts, and metallocene based compounds with at least an anion selectedfrom the group consisting of SbF₆ ⁻, PF₆ ⁻, B(C₆F₅)₄ ⁻, [B(CF₃)₄]⁻,tetrakis(3,5-difluoro-4-methoxyphenyl)borate, perfluoroalkylsulfonates,perfluoroalkylphosphates, tris[(perfluoroalkyl)sulfonyl]methides, and[(C₂F₅)₃PF₃]⁻.

Examples of cationic photo-initiators useful for curing at 300-475 nmwithout a sensitizer include4-[4-(3-chlorobenzoyl)phenylthio]phenylbis(4-fluorophenyl)sulfoniumhexafluoroantimonate,4-[4-(3-chlorobenzoyl)phenylthio]phenylbis(4-fluorophenyl)sulfoniumtetrakis(pentafluorophenyl)borate,4-[4-(3-chlorobenzoyl)phenylthio]phenylbis(4-fluorophenyl)sulfoniumtetrakis(3,5-difluoro-4-methyloxyphenyl)borate,4-[4-(3-chlorobenzoyl)phenylthio]phenylbis(4-fluorophenyl)sulfoniumtetrakis(2,3,5,6-tetrafluoro-4-methyloxyphenyl)borate,tris(4-(4-acetylphenyl)thiophenyl)sulfoniumtetrakis(pentafluorophenyl)borate (Irgacure® PAG 290 from BASF),tris(4-(4-acetylphenyl)thiophenyl)sulfoniumtris[(trifluoromethyl)sulfonyl]methide (Irgacure® GSID 26-1 from BASF),tris(4-(4-acetylphenyl)thiophenyl)sulfonium hexafluorophosphate(Irgacure® 270 from BASF), and HS-1 available from San-Apro Ltd.

Preferred cationic photo-initiators include, either alone or in amixture: bis[4-diphenylsulfoniumphenyl]sulfide bishexafluoroantimonate;thiophenoxyphenylsulfonium hexafluoroantimonate (available as Chivacure1176 from Chitec), tris(4-(4-acetylphenyl)thiophenyl)sulfoniumtetrakis(pentafluorophenyl)borate (Irgacure® PAG 290 from BASF),tris(4-(4-acetylphenyl)thiophenyl)sulfoniumtris[(trifluoromethyl)sulfonyl]methide (Irgacure® GSID 26-1 from BASF),and tris(4-(4-acetylphenyl)thiophenyl)sulfonium hexafluorophosphate(Irgacure® 270 from BASF), [4-(1-methylethyl)phenyl](4-methylphenyl)iodonium tetrakis(pentafluorophenyl)borate (available as Rhodorsil 2074from Rhodia),4-[4-(2-chlorobenzoyl)phenylthio]phenylbis(4-fluorophenyl)sulfoniumhexafluoroantimonate (as SP-172 from Adeka), SP-300 from Adeka, andaromatic sulfonium salts with anions of (PF_(6-m)(C_(n)F_(2n+1))_(m))⁻where m is an integer from 1 to 5, and n is an integer from 1 to 4(available as CPI-200K or CPI-200S, which are monovalent sulfonium saltsfrom San-Apro Ltd., TK-1 available from San-Apro Ltd., or HS-1 availablefrom San-Apro Ltd.).

Optional Particulate Filler

In certain embodiments, the composition comprises a particulate filler.Examples of particulate fillers include both organic and inorganicparticulate fillers. The particulate filler may possess a surfacefunctionality or not, the surface functionality comprising apolymerization group that is capable of (co)polymerization with thefirst network-forming component or second network-forming component. Theparticulate filler may be micro or nano-particles comprising organicparticles, such as core-shell particles, inorganic particles, pigments,or plasticizers. In an embodiment, the particulate filler comprises aninorganic filler, such as SiO₂, AlO₂, TiO₂, ZnO₂, SnO₂, Am—SnO₂, ZrO₂,Sb—SnO₂, Al₂O₃, or carbon black. In an embodiment, the particulatefiller comprises an organic filler, such as polyurethane particles,polystyrene particles, poly(methyl methacrylate) particles,polycarbonate particles, or core-shell particles.

In an embodiment, the particulate filler comprises a polymerizable groupthat is able to (co)polymerize with the polymerizable groups of theTPA-based polyester. In an embodiment, the particulate filler comprisesa polymerizable group that is able to (co)polymerize with thepolymerizable groups of the one or more second network compounds. In anembodiment, the particulate filler comprises a polymerizable groupcomprising acrylate, methacrylate, epoxy, oxetane, hydroxyl, itaconate,vinyl ether, allyl ether, maleate, or fumarate. In an embodiment, theparticulate filler comprises a polymerizable group comprising acrylate,methacrylate, epoxy, oxetane, hydroxyl, or itaconate. In an embodiment,the particulate filler comprises a polymerizable group comprisingacrylate or methacrylate. In an embodiment, the particulate fillercomprises a polymerizable group comprising epoxy, oxetane or hydroxyl.

In an embodiment, the particulate filler comprises an impact modifier.Examples of impact modifiers are elastomer particles. In an embodiment,the impact modifying components, which can be dispersed into thecomposition, are elastomers based on copolymers of ethylene or propyleneand one or more C₂ to C₁₂ α-olefin monomers.

Examples of such are ethylene/propylene copolymers or ethylene/propylenecopolymers, optionally containing a third copolymerizable diene monomer(EPDM), such as 1,4-hexadiene, dicyclopentadiene, di-cyclooctadiene,methylene norbornene, ethylidene norbornene and tetrahydroindene;ethylene/α-olefin copolymers, such as ethylene-octene copolymers andethylene/α-olefin/polyene copolymers.

In an embodiment, the particulate filler comprises polybutadiene,polyisoprene, styrene/butadiene random copolymer, styrene/isoprenerandom copolymer, acrylic rubbers (e.g. polybutylacrylate),poly(hexamethylene carbonate).

Elastomer particles may be prepared by a variety of means, including byisolation from a latex made via emulsion polymerization. The averagesize of these elastomer particles is preferably between about 10 nm andabout 10 μm. In an embodiment, the average size of the elastomerparticles if from 10 nm to 1 μm.

Optionally, the elastomer may be modified to contain reactive groupsthat (co)polymerize with the first or second network-forming component.This modification can be introduced by reactive grafting or bycopolymerization. Commercial examples of the latter are Lotader randomethylene/acrylate copolymers AX8840 (glycidyl methacrylate/GMAmodified), AX8900 and AX8930 (GMA and maleic anhydride modified/MA)produced by Arkema.

Optionally, a shell may be present on the particles that can beintroduced, e.g., via grafting or during a second stage of emulsionpolymerization. Examples of such particles are core-shell impactmodifier particles that contain a rubber core and a glassy shell.Examples of core materials are polybutadiene, polyisoprene, acrylicrubber (e.g. polybutylacrylate rubber), styrene/butadiene randomcopolymer, styrene/isoprene random copolymer, or polysiloxane. Examplesof shell materials or graft copolymers are (co)polymers of vinylaromatic compounds (e.g. styrene) and vinyl cyanides (e.g.acrylonitrile) or (meth)acrylates (e.g. MMA).

Optionally, polymerizable groups can be incorporated into the shell bycopolymerization, such as copolymerization with glycidyl methacrylate,or by treatment of the shell to form reactive functional groups.

Commercially available products of these core-shell type elastomerparticles are Resinous Bond RKB (dispersions of core-shell particles inepoxy manufactured by Resinous Chemical Industries Co., Ltd.),Durastrength D400, Durastrength 400R (manufactured by Arkema Group),Paraloid EXL-2300 (non-functional shell), Paraloid EXL-2314 (epoxyfunctional shell), Paraloid EXL-2600, Paraloid EXL-3387 and ParaloidKM-365 (manufactured by Dow), Genioperl P53, Genioperl P23, GenioperlP22 (manufactured by Wacker Chemical), Kane Ace MX products(manufactured by Kaneka), and the like.

Other examples of such elastomer particles are crosslinkedpolyorganosiloxane rubbers that may include dialkylsiloxane repeatingunits, where “alkyl” is C₁-C₆ alkyl. The particles may be modified toinclude reactive groups, preferably on the surface of the particles.

Examples of polyorganosiloxane elastomer particles that are commerciallyavailable are Albidur EP 2240(A), Albidur EP 2640, Albidur VE 3320,Albidur EP 5340, Albidur EP 5640, and Albiflex 296 (dispersions ofparticles in epoxy or vinyl ether resins, Hanse Chemie, Germany),Genioperl M41C (dispersion in epoxy, Wacker Chemical), Chemisnow MXSeries and MP Series (Soken Chemical and Engineering Co.).

In an embodiment, two different diameters of impact modifiers are usedin a certain ratio. In an embodiment, the composition of impactmodifiers is about a 7 to 1 ratio of diameter (e.g. 140 nm particles vs.a 20 nm particles) and about a 4 to 1 ratio of wt %. In anotherembodiment, the composition of impact modifiers is about a 5 to 1 ratioof diameter and about a 4 to 1 ratio of wt %. In another embodiment thecomposition of impact modifiers is about a 5 to 1 ratio of diameter andabout a 6 to 1 ratio of wt %.

In an embodiment, the particulate filler is present in the compositionin an amount of 1 wt % or more, 5 wt % or more, 10 wt % or more, 15 wt %or more, 20 wt % or more, 30 wt % or more, 40 wt % or more, or 50 wt %or more, based on the total weight of the composition. In an embodiment,the particulate filler is present in the composition in an amount of 90wt % or less, 80 wt % or less, 70 wt % or less, 60 wt % or less, 50 wt %or less, 40 wt % or less, 30 wt % or less, or 20 wt % or less, based onthe total weight of the composition.

Further Optional Components

Additional components that may be present in the composition includestabilizers, such as viscosity stabilizers or light stabilizers, UVabsorbers, dyes, pigments, plasticizers, surfactants, antioxidants,wetting agents, photosensitizers, defoamers, flame retardants, silanecoupling agents, acid scavengers, accelerators for a thermal initiator,and/or bubble breakers.

In an embodiment, the polymerizable composition comprises anon-particulate impact modifier. In an embodiment, the non-particulateimpact modifier comprises a block copolymer that is soluble in thecomposition or dispersed as micelles. In an embodiment, the blockcopolymer comprises ethylene/acrylate random copolymers and acrylicblock copolymers, styrene/butadiene/(meth)acrylate (SBM)block-copolymers, styrene/butadiene block copolymer(styrene-butadiene-styrene block copolymer (SBS),styrene-isoprene-styrene block copolymer (SIS) and their hydrogenatedversions, SEBS, SEPS), and (SIS) and ionomers.

Examples of commercial block copolymers are Kraton (SBS, SEBS, SIS, SEBSand SEPS) block copolymers produced by Shell, Nanostrength blockcopolymers E20, E40 (SBM type) and M22 (full-acrylic) as produced byArkema, Lotryl ethyl/acrylate random copolymer (Arkema), Ethyleneoxide-butylene oxide block copolymers produced by Olin Chemicals, andSurlyn ionomers (Dupont).

The non-particulate impact modifier may comprise a polymerizable group.In the case that the non-particulate impact modifier comprises apolymerizable group, the non-particulate impact modifier may be afurther first network monomer, oligomer, or polymer or may be a secondnetwork compound, depending on the polymerizable groups of the TPA-basedpolyester.

The composition may optionally comprise a solvent. A solvent does nothave any polymerizable groups. The solvent may be a mixture of more thanone solvent. Examples of solvents include alcohols, ketones, esters, orethers; preferably an alcohol such as methanol, ethanol or iso-propanol.In an embodiments, the composition comprises 50 wt % or less of solvent,based on the total weight of the composition, such as 40 wt % or less,30 wt % or less, 20 wt % or less, 10 wt % or less, 5 wt % or less, or 0wt %.

Applications

In accordance with an embodiment of the invention, an article may beformed by polymerizing the composition. In an embodiment, a film formedby polymerizing 90% or more of total the polymerizable groups in thecomposition has a tensile modulus as measured at 150° C. of from 3, from5, from 7, from 10, from 15, or from 20 MPa to 50, to 45, or to 40 MPa.In an embodiment, a film formed by polymerizing 90% or more of total thepolymerizable groups in the composition has a yield stress at 23° C. offrom 50 to 90 MPa, and an elongation at break at 23° C. of greater than3%, optionally in combination with the above tensile modulus as measuredat 150° C. In an embodiment, a film formed by polymerizing 90% or moreof the total polymerizable groups in the composition has a tensilemodulus at 23° C. of from 2000 to 3500 MPa. Tensile modulus at 150° C.is determined by DMTA in accordance with ASTM D5026. Tensile modulus at23° C., yield stress at 23° C., and elongation at break at 23° C. aredetermined according to ISO 37:2011 Rubber, vulcanized orthermoplastic—Determination of tensile stress-strain properties.

The amount of the composition that is polymerized is determined using IRby the following method. Samples are measured on a Perkin Elmer SpectrumOne equipped with a Universal ATR Sampling accessory. Peak heights arenormalized to the carbonyl peak at 1727 cm⁻¹, or another peak that doesnot change. Conversion is calculated using the following formula: %conversion=((A₀−A_(t))/A₀)*100%, wherein A₀ is the normalized absorbanceprior to cure and A_(t) is the normalized absorbance during curing. Forexample, conversion of acrylate bonds may be measured by following thedecrease of IR absorbance peak at 810 cm⁻¹.

Preferred applications of the composition include additive fabricationprocesses. Additive fabrication processes, sometimes known asthree-dimensional printing, utilize computer-aided design (CAD) data ofan object to build three-dimensional objects. These three-dimensionalobjects may be formed from liquid resins, powders, or other materials.The CAD data is loaded into a computer that controls a machine thatforms and binds layers of materials into desired shapes. The desiredshapes correspond to portions of a three-dimensional object, such asindividual cross-sections of the three-dimensional object. The desiredshapes may be formed by selectively dispensing the composition, such asin an inkjet printing system, into the desired shape and then curing ormelting the composition if necessary. Another way of forming the desiredshapes is by selectively curing or melting the material into the desiredshape out of a large bed or vat of material, such as instereolithography or selective laser sintering.

In an embodiment, an article is formed by forming a layer from a firstcomposition comprising the TPA-based polyester and selectivelydispensing a second composition comprising one or more first networkmonomers onto the first composition in accordance with the shape of aportion of a three-dimensional object. The one or more first networkinitiators may be present either in the layer of TPA-based polyester, inthe composition comprising the one or more first network monomers, orboth. The composition comprising the one or more first network monomersmay be selectively dispensed by jetting, for example by inkjet.

In an embodiment, a method of forming a three-dimensional objectcomprises the steps of forming a layer of the composition, curing thelayer with radiation to form a desired shape, and repeating the steps offorming and curing a plurality of times to obtain a three-dimensionalobject. In an embodiment, a method of forming a three-dimensional objectcomprises the steps of selectively dispensing the composition, curingthe composition with radiation to form a desired shape, and repeatingthe steps of selectively dispensing and curing a plurality of times toobtain a three-dimensional object. In an embodiment, a method of forminga three-dimensional object comprises the steps of forming a layer of thecomposition, selectively curing the layer with radiation to form adesired shape, and repeating the steps of forming and selectively curinga layer of the composition a plurality of times to obtain athree-dimensional object.

In an embodiment, the viscosity of the composition at 30° C. is 4000 cpsor less, 3000 cps, or less, 2000 cps or less, 1500 cps or less, or 1200cps or less. The viscosity of the composition at 30° C. is typically 300cps or more.

In an embodiment, the composition is present as a liquid at the timethat the polymerization reaction is initiated by the application oflight or heat. In an embodiment, the liquid composition possesses atemperature of from 25° or more at the time that polymerization isinitiated, such as 30° C. or more, 35° C. or more, 40° C. or more, or45° C. or more. The temperature is typically 200° C. or less, such as180° C. or less. In an embodiment, the temperature is 150° C. or less,100° C. or less, 80° C. or less, or 50° C. or less.

In an embodiment, an article can be formed by first introducing thepolymerizable composition into a mold or coating the polymerizablecomposition on a surface.

In an embodiment, the composition is present as separate parts in a kitof materials. The kit comprises a particulate sub-composition comprisingthe TPA-based polyester, and a liquid sub-composition comprising the oneor more first network monomers. The first network initiator may bepresent with either the TPA-based polyester or the one or more firstnetwork monomers, or as a separate part of the kit.

In an embodiment, the particulate sub-composition or the liquidsub-composition further comprises an absorber. An absorber absorbselectromagnetic radiation. In an embodiment, the absorber absorbs one ormore of infrared light, near infrared light, and visible light. Thewavelengths that are absorbed by the by the absorber should overlap withthe wavelengths of the electromagnetic radiation. In an embodiment, theabsorber is a pigment, a dye, metallic particles, or carbon black.

The particulate sub-composition may further comprise additives, such asdyes, pigments for coloration, or absorbers. In an embodiment, theparticulate sub-composition further comprises a particulate filler. Inan embodiment, the particulate filler comprises a polymerizable groupthat is able to (co)polymerize with the polymerizable groups of theTPA-based polyester. In an embodiment, the particulate sub-compositionhas a mean particle diameter of from 10 to 100 μm as measured by laserdiffraction in accordance with ISO13320 (2009). In an embodiment, theparticulate sub-composition has a mean particle diameter of from 30 to80 μm as measured by laser diffraction in accordance with ISO13320(2009).

The liquid sub-composition may further comprise additives such asabsorbers, reflectors, dyes, or pigments for coloration.

In an embodiment, the composition or liquid sub-composition furthercomprises a dispersing medium, such that certain components of thecomposition are dispersed in the dispersing medium. In an embodiment, atleast the one or more first network monomers are dispersed in thedispersing medium. In an embodiment, at least one or more first networkmonomers and one or more first network initiators are dispersed in thedispersing medium. When present, the dispersing medium is typicallypresent in an amount of from 20 to 70 wt %, based on the total weight ofthe composition, or from 20 to 80 wt % based on the liquidsub-composition. The dispersing medium is a non-solvent, preferablywater. When water is the dispersing medium, it is preferred that nocationically curable components are present in the composition. In anembodiment, the composition comprises 50 wt % or more of water, based onthe total weight of the composition. An article or coating may be formedby forming a layer of the composition, if necessary evaporating thedispersing medium, and polymerizing the composition.

Some potential applications of articles disclosed herein include asmolded articles, shoe soles, eyeglasses, three-dimensional objectsformed by additive fabrication processes, coatings for optical fibers,medical devices or coatings on medical devices, other coatings, andpaints.

Examples

The following examples are included to further elucidate the presentinventions, but should in no way be seen as limiting their scope.

Polyester Synthesis

A reactor vessel fitted with a thermometer, a stirrer and a distillationdevice for the removal of water formed during the synthesis, was filledwith a tin catalyst and 1,2-propanediol and trimethylolpropane ifapplicable. The vessel was heated up until the mixture reached 110° C.after which terephthalic acid was added and under a nitrogen flow. Thetemperature was gradually increased to 245° C. while distilling of thereaction water until the acid number of the precursor of the polyesterwas below 20 mg KOH/g and the hydroxyl value was measured. If needed thereaction mixture was corrected with 1,2-propanediol (15-20 mg KOH/gabove the desired hydroxyl value) at 200° C. and heated for another hourat 245° C. before proceeding to the vacuum step. At 200° C. reducedpressure was applied until the polyester reached an acid value below 5mg KOH/g and the desired hydroxyl value. To further reduce the acidvalue ethylenecarbonate was added at 190° C. and the amount was based onreducing the measured acid value to zero. The temperature was maintainedat 200° C. for one hour after which vacuum was applied for 15 minutesand the mixture was discharged onto an aluminum foil kept at roomtemperature. The chemical makeup of the polyesters are shown in Tables0.1 and 0.2.

TABLE 0.1 Polyesters Tere- phthalic 1,2- Trimethylol- Ethylene- Tin-acid propanediol propane carbonate catalyst Experiment [g] [g] [g] [g][g] 003886-001 2196.5 1120.0 0 22.0 2.8 003245-072 3261.6 1888.9 178.927.8 3.4 003245-075 2260.2 1151.5 140.9 13.9 2.3

TABLE 0.2 Polyesters OH AV [mg [mg Mn function- Tg Sample code KOH/g]KOH/g] (g/mol)* ality [° C.] NBK-003886-001 38.7 3.7 2672 2 64.8NBK-003245-072 130.6 1.5 977 2.3 29.3 NBK-003245-074 64.5 2.3 1930 2.357.1 NBK-003245-075 71.8 1.8 2060 2.7 59.1 NBK-003245-095 83.2 2.0 18482.9 56.9 NBK-003245-096 108.4 2.8 1320 2.7 46.5 NBK-003245-098 111.5 2.01406 2.9 46.8 NBK-003245-124 120.5 3.9 1217 2.7 37.3 *Theoretical Mn

AV and OH Measurement

The acid (AV) and hydroxyl (OH) values of the polyester were determinedtitrimetrically according to ISO 2114-2000 and ISO 4629-1978.

Tg Measurement

The glass transition temperature of the resin (T_(g) in ° C.) wasmeasured via Differential Scanning calorimetry (DSC) on a TA instrumentsDSC Q20 apparatus, in an atmosphere of N₂ calibrated with indium. Theprocessing of the signal (DSC thermogramme, Heat Flow vs. Temperature)was carried out using Universal Analysis 2000 software version 4.5aprovided by TA instruments, as described herein after:

A sample of 10±3 mg was weight and placed in the DSC cell. The samplewas heated to 150° C. and the temperature was kept at 150° C. for 10minutes; upon 10 minutes the sample was cooled to 0° C. as fast aspossible followed by an equilibration. The sample was heated up to 100°C. at a heating rate of 5° C./minute (thermograph). The thermograph wasprocessed as the Y axis of the thermograph representing the heat flowhas exotherm up and the inflection point temperature of the glasstransition signal was taken as Tg.

Functionalization of Polyesters with Methacroyl Chloride

The polyesters presented in Table 0.2 were functionalized withmethacryloyl chloride to yield a methacrylate functional TPA-polyesters.

NBK-003886-001

MH-01245-029NBK-003245-072

MH-01245-080NBK-003245-075

MH-01245-083NBK-003245-095

MH-01245-87NBK-003245-096

MH-01245-84 and MH-01245-102NBK-003245-098

MH-01245-86NBK-003245-124

MH-01245-112

Next a typical functionalization experiment with methacryloyl chloridewill be described. All above described polyesters are functionalized isthe same manner.

MH-01245-029:

NBK-003886-001 (99 g, 39.7 mmol) was weight in a 500 ml 4-neck RB flask.After weighing, the RB flask is fitted with a thermometer, stirring bar,N₂ inlet and a septum. The RB flask was flushed with N₂ for a minimum of30 minutes. 250 ml dichloromethane (anhydrous) was injected into the RBflask, with the use of 50 ml glass syringe, through the septum. Afterwhich the oligomer is let to dissolve at room temperature. Once theoligomer is completely dissolved, triethylamine (24.19 mL, 174 mmol) wasadded to the reaction mixture, followed by a drop wise addition ofmethacryloyl chloride (13.46 mL, 138 mmol). During the addition, anisotherm of approx. 5° C. was observed. The flask was cooled with icewater to control the exothermic reaction. The reaction mixture wasanalysed after 2.5 hours. The sample was filtered and dried at RT byapplying vacuum. The reaction mixture was allowed to stir under N₂conditions overnight at room temperature.

H-NMR was inconclusive, therefore an additional of 10% triethylamine andMethacryloylchloride was added. (1.73 grams of triethylamine and 1.35grams of methacryloylchloride) to drive the reaction to completion overa time frame of 3 hours and 15 minutes.

The reaction mixture was filtered over a filter (carton) to remove theformed salt. Due to evaporation of the DCM, more salt was precipitatingout of the solution. The mixture was cooled in the fridge for 30 minutesand filtered again to remove the salt. The buchner flask and funnel werewashed with (2 times 25 mL) dichloromethane. Subsequently the mixturewas precipitated in a 5 L Schott-bottle by dropwise addition in Methanol(4.7 Liter) at room temperature. DCM was used to rinse the droppingfunnel and flask.

The precipitate was left overnight in the flask without stirring. Nextday, the supernatant was removed and the precipitate was washed one timewith methanol (200 mL) for 1 hour. Methanol was removed and THF (BHTstabilised, 200 mL) was added to dissolve the polymer. The polymersolution was stored in the fridge over the weekend.

A test sample was taken to determine the OH-conversion. Therefore asample was analysed before and after addition of TFAA (H-NMR). Thesesamples showed no OH-groups.

After dissolving the oligomer, the product was poured onto a teflonbeaker after which, the THF was allowed to evaporate for 24 hours. Afterevaporation to air, the trays were placed in a vacuum oven at roomtemperature for 24 hours to remove the remaining THF. Subsequently, thepolymer was dried 24 hours at 50° C. to remove residual solvent andtriethylamine. The resulting yield was 86.5 grams.

H-NMR analysis showed still residual triethylamine and THF. Therefore,the sample was further dried at 70° C. for two hours afterwhich thetemperature of the oven was shut down, allowing it to cool to roomtemperature overnight.

The yield was 86.0 g, Et3N content ˜0.8% mass/mass. This sample isreferred to as MH-01245-029.

MH-01245-080:

003245-072 (227 g, 232 mmol) was weighed in a 500 ml 4-neck RB flask.After weighing, the RB flask is fitted with a thermometer, stirring bar,N₂ inlet and a septum.

CH₂Cl₂ (anhydrous) (250 mL) injected into the RB flask, with the use of50 ml glass syringe, through the septum, after which the polyester isleft to dissolve at room temperature. The flask was cooled with icewater to control the exothermic reaction.

Once the polyester is completely dissolved, triethylamine (78 mL, 558mmol) is added to the reaction mixture, followed by a drop wise additionof methacryloyl chloride (49.9 mL, 511 mmol). During the addition, anisotherm of approx. 20° C. was observed. Due to bad mixing thetemperature increased to max 35° C. The reaction mixture was analyzedafter 2 hours. The sample was filtered and dried at RT by applyingvacuum. The reaction was complete. The reaction mixture was stirredovernight at room temperature.

The reaction mixture was then cooled for 30 minutes in a freezer. Thereaction mixture was filtered over a filter to remove the formed salt.The Büchner flask and funnel were washed with dichloromethane (2 times20 mL). Subsequently, the mixture was precipitated in a 5 LSchott-bottle by dropwise addition in Methanol (4.5 Liter) at roomtemperature. DCM (40 mL) was used to rinse the dropping funnel andflask.

The precipitate was left for 2 hours in the flask while stirring. Thesupernatant was removed by decantation and the precipitate was washedone time with methanol (200 mL) for 1 hour. Methanol was removed and theprecipitate dried overnight under reduced pressure in oven at roomtemperature.

THF (1400 ml) was added to dissolve the polyester. After dissolving thepolyester, the product was filtered to remove salt.

After filtration most of the THF was removed with rotavapor and pouredinto two Teflon® beakers. The remaining THF was removed in an oven atroom temperature with max vacuum overnight. Subsequently, the polyesterwas dried 4 hours at 35° C. to remove residual solvent andTriethylamine. The yield was 75 g.

MH-01245-083:

003245-075 (100 g, 48.5 mmol) was weighed in a 500 ml 4-neck RB flask.After weighing, the RB flask is fitted with a thermometer, stirring bar,N₂ inlet and a septum.

CH₂Cl₂ (anhydrous) (250 mL) injected into the RB flask, with the use of50 ml glass syringe, through the septum. After which the polyester isleft to dissolve at room temperature. The flask was cooled with icewater to control the exothermic reaction.

Once the polyester is completely dissolved triethylamine (42.7 mL, 306mmol) is added to the reaction mixture, followed by a drop wise additionof methacryloyl chloride (27.5 mL, 282 mmol). During the addition, anisotherm was observed; max temperature was 20° C. The reaction wasanalyzed after 2 hours of stirring. 10% triethylamine and 10%methacryloylchloride was additionally added to drive the reaction tocompletion.

The reaction was stirred (50 RPM) overnight at room temperature. Thereaction was analyzed via H-NMR and it was observed that the reactionwas completed.

The reaction mixture was cooled for 30 minutes in freezer. The reactionmixture was filtered over a filter to remove the formed salt. TheBüchner flask and funnel were washed with (2 times 20 mL)dichloromethane. Subsequently, the mixture was precipitated in a 5 LSchott-bottle by dropwise addition in Methanol (4.5 Liter) at roomtemperature. DCM (40 mL) was used to rinse the dropping funnel andflask.

The precipitate was left for 2 hours in the flask while shaking. Thesupernatant was removed by decantation and the precipitate was washedone time with methanol (200 mL) for 1 hour. Methanol was removed and theprecipitate dried overnight under reduced pressure in an oven at roomtemperature.

THF (200 ml) was added to dissolve the polyester. After dissolving thepolyester, the product was filtered to remove salt.

After filtration, most of the THF was removed with rotavapor and pouredinto two Teflon® beakers. The remaining THF was removed in an oven atroom temperature for 4 hours and subsequently the polyester was driedfor 4 hours at 50° C. to remove residual solvent and triethylamine. Theyield was 85 g. P-NMR showed no primary or secondary alcohol groups.

Alternative Functionalization Method Via IPDI-HEMA Route

An alternative way to functionalize the polyester (e.g.,NBK-003245-124), is to perform an urethane synthesis reacting thepolyester with isophorone diisocyanate and hydroxy ethyl methacrylate inthe preferred reactive diluent. This process yields the polyesterurethane methacrylate in reactive diluent, in this case benzylmethacrylate. Into a glass reactor equipped with lean air, 979.5 gisophorone diisocyanate (1,463 mol), 3 g butylated hydroxy toluene (500ppm), 1200 g benzyl methacrylate and 3 g dibutyl tin dilaurate is addedand allowed to mix for 5 minutes. Over a time frame of 3 hours, 573.5 ghydroxy ethyl methacrylate is added whilst cooling the reactor. After 1hour 1200 g benzyl methacrylate and 3 g dibutyl tin dilaurate andallowed to mix for 10 minutes. Then 2038.0 g TPA-polyester(NBK-003245-124) is added and the mixture is heated to 85° C. Thereaction is continued over approx. 16 hours at 85° C. Subsequently, thereactor is discharged over a 125 micron filter. The resulting materialis a 60/40 mixture of polyester urethane methacrylate in benzylmethacrylate (NBK-003068-110).

Composition Formation

The solid polyester is added into a UV-protected vial supplied with ascrew cap. Then the reactive diluent is added. The mixture is stirredand heated at 80° C. in order to dissolve. Once the mixture ishomogeneous, Irgacure 819 is added (2% of total mass) and allowed todissolve.

Curing

Glass was pre-treated with a fluor silane and allowed to react overnightat 120° C. The films are made with a doctor blade (500 μm) on thepre-treated glass and then cured on a Fusion UV-rig equipped withnitrogen flow under a D-bulb at 30° C. Total UV-dose was approximately 7J/cm² at 13 W/cm² (sum of UVA, UVB and UVC).

80° C. cure conditions: Castings were prepared by sandwichingpre-treated glass plates with 1 mm spacers. The formulation ispre-heated to 80° C. and subsequently poured into the casting. UV-curewas performed with a static UV-source equipped with an H-bulb for 3minutes. Total UV-dose was approximately 30 J/cm² at 0.2 W/cm².

Thermal post-cure: In order to ensure complete conversion of thematerials, all samples were post cured at 100° C. overnight in air priorto measuring the mechanical properties.

DMTA

Samples with a width of approximately 2 mm are punched out of the curedfilms. The thickness is measured with a calibrated Heidenhain thicknessmeter. The dynamic mechanical analyses are carried out in accordancewith ASTM D5026 using a RSA-G2 test system at a frequency of 1 Hz andover a temperature ranging from −100° C. to 200° C. with a heating rateof 5° C./min. During the measurements, the storage modulus (E′), lossmodulus (E″) and tangent delta (tan δ) are determined as a function oftemperature.

Tensile Tests

Tensile properties are measured according to the international standardISO 37 (3^(rd) Edition 1994-05-15) “Rubber, vulcanized orthermoplastic—Determination of tensile stress-strain properties” on aZwick digital tensile machine type Z010. The parameters of the tensiletest are shown in Table 0.3.

TABLE 0.3 Tensile Test Machine Parameters Machine Zwick Z010 table 2Control & analysis Zwick software, TestXpert II Load-cell 2.5 kNloadcell Displacement MultiXtense Grips fixture 1 kN pneumatic gripsE-modulus speed 1 mm/min Modulus determination strain between 0.05 and0.25% Test speed tensile 5 mm/min Grip-to grip distance 54 mm L0 25 mmPre-load 0.5 N Tensile standard ISO 527 Tensile specimen type 1BA

Example 1

A composition is prepared consisting of 70 parts by weight of TPA-basedpolyester MH-01245-029 (functionality 2, Mn ˜2500 g/mol), 30 parts byweight of (hydroxylethyl methacrylate) HEMA, and 2 parts by weightIrgacure® 819. The sample is cured at 80° C. DMTA Results are shown inTable 1.1. Tensile Data is shown in FIG. 1 and reported in Table 1.2.

TABLE 1.1 Example 1 DMTA Results Tg (E″ max, ° C.) 90 Cross-link Densityas determined by 3 tensile modulus at 150° C. (MPa)

TABLE 1.2 Example 1 Tensile Results Tensile Modulus (GPa) 2.7 YieldStress (MPa) 65

Example 2

A composition is prepared consisting of 60 parts by weight of TPA-basedpolyester MH-01245-083 (functionality 2.7, Mn ˜2000 g/mol), 40 parts byweight of HEMA, and 2 parts by weight Irgacure® 819. The sample is curedat 30° C. DMTA Results are shown in Table 2.1. Tensile Data is shown inFIG. 2 and reported in Table 2.2.

TABLE 2.1 Example 2 DMTA Results Tg (E″, ° C.) 90 Cross-link Density asdetermined by 7 tensile modulus at 150° C. (MPa)

TABLE 2.2 Example 2 Tensile Results Tensile Modulus (GPa) 2.5 YieldStress (MPa) 60

Examples 3-5

Various 60/40 (i.e. 60 parts per weight of TPA-based polyester, 40 partsper weight of HEMA, and 2 parts per weight of photoinitiator Irgacure819) compositions of TPA-polyesters with varying functionality andmolecular weight were next created. The Tg and cross-link density asdetermined by tensile modulus at 150° C. of each (Example 3:MH-01245-087, with a functionality of 2.85, Mn ˜2050 g/mol; Example 4:MH-01245-084, functionality 2.62, Mn ˜1500 g/mol; and Example 5:MH-01245-086, functionality 2.84, Mn ˜1600 g/mol) is shown in table 2.3below.

TABLE 2.3 Tg and Tensile Results of Examples 3-5 Example 3 Example 4Example 5 Tg (E″ max, ° C.) 89 84 82 Cross-link Density as 7 6 6determined by tensile modulus at 150° C. (MPa)

Examples 6-11

The effect of various first network monomers was next determined bycreating various mixtures including 60 parts per weight of TPA-basedpolyester MH-01245-084 (having a functionality of 2.62 and Mn of ˜1500g/mol), 40 parts per weight of the respective diluent (Example 6:isobornyl methacrylate or IBOMA; Example 7: benzyl methacrylate or BMA;Example 8: cyclohexyl methacrylate or CHMA; Example 9:tetrahydrofurfuryl methacrylate or THFMA; Example 10: hydroxy propylmethacrylate or HPMA; and Example 11: hydroxy ethylmethacrylate orHEMA), and 2 parts per weight of photoinitiator Irgacure 819)compositions. Again the Tg and cross-link density as determined bytensile modulus at 150° C. of each was determined and is recorded intable 2.4 below.

TABLE 2.4 Tg and Tensile Results of Examples 6-11 Ex. 6 Ex. 7 Ex. 8 Ex.9 Ex. 10 Ex. 11 Tg (E″ max, ° C.) 109 78 98 78 78 84 Cross-link Densityas 6 5 5 6 5 6 determined by tensile modulus at 150° C. (MPa)

Examples 12-15

The effect on network structure of materials that contained acationically polymerizable fraction was observed in Examples 12-15. Thecationic portion is Somos® NeXt (available from DSM) centrifuged toremove any solid particles (0763-119). The compositions used in theseexperiments (which again determined Tg and cross-link density asdetermined by tensile modulus at 150° C.) is reported in Table 2.5, withthe results reflected in 2.6.

TABLE 2.5 Composition of Examples 12-15 Component Ex. 12 Ex. 13 Ex. 14Ex. 15 NBK-03068-110 95 90 80 70 0763-119 5 10 20 30 Irgacure 819 2 2 22

TABLE 2.6 Tg and Tensile Results of Examples 12-15 Component Ex. 12 Ex.13 Ex. 14 Ex. 15 Tg (E″ max, ° C.) 79 66 50 31 Cross-link Density as 5 54 4 determined by tensile modulus at 150° C. (MPa)

Example 16

Finally, an experiment was conducted whereby the suitability of acomposition according to the present invention was tested in a simulatedpowder/binder 3D printing process. Accordingly, 15 grams of polyesterwas sieved with 212 micron sieve. 4 grams of this sieved powder wasdivided homogeneously on a plate. In the mean time 3.54 grams of THFMAand 89 mg BAPO (bis acyl phosphine oxide) was mixed. This mixture wasspreaded over the plate and allowed to “mix”. After 15 minutes at 40° C.almost everything “dissolved”. The plate was then UV-cured by means ofFusion H-bulb for 1 minute. A DMTA graph was plotted, with the resultssummarized in Table 2.7.

TABLE 2.7 Tg and Tensile Results of Example 16 Component Ex. 16 Tg (E″max, ° C.) 88 Cross-link Density as 8 determined by tensile modulus at150° C. (MPa)

Discussion of Results

As can be seen in the experiments relative to Examples 1 and 2, theformed network achieves a high Tg (approx. 90° C.) and low cross-linkdensity (3-10 MPa). These values are superior relative to existingmaterials used in stereolithography. Generally, stereolithographymaterials behave in a relatively more brittle fashion, commonly with ayield stress significantly higher than 70 MPa, whereas the formednetwork achieves a yield stress of 65 MPa.

The experiments relative to Examples 3-5 reinforce that the desirednetwork structure can be achieved with different molecular weights andfunctionalities.

The experiments relative to Examples 6-11 reinforce that the technicaleffect of compositions of the current invention is achieved with a widevariety of known diluents/first network monomers. In particular, thenetwork density for all diluents is substantially similar, whereas theTg is dominated by the homopolymer Tg of the mono-functional diluentitself.

The experiments relative to Examples 12-15 reinforce that the technicaleffect of compositions of the current invention may be achieved with theinclusion of a cationically-polymerizable network forming component aswell.

The process and experiments relative to Example 16 demonstrates thesuitability of compositions according to the present invention inpowder/binder type 3D printing applications.

Supplementary Description of Certain Exemplary Embodiments

-   -   1) A composition for forming a three-dimensional object via an        additive fabrication process comprising:        -   a. from 30 to 100 wt %, based on the total weight of the            composition, of a first network-forming component consisting            of:            -   i. from 19.95 to 80 wt %, based on the total weight of                the first network-forming component, of a TPA-based                polyester comprising a backbone and having a number                average of at least 2 polymerizable groups, wherein the                backbone comprises the reaction product of a                terephthalic acid and a polyol, wherein the                polymerizable groups comprise acrylate, methacrylate,                epoxy, oxetane, hydroxyl, itaconate, vinyl ether, allyl                ether, maleate, or fumarate, and wherein the TPA-based                polyester has a number average molecular weight of from                800 to 10000 g/mol and a Tg of 40° C. or more;            -   ii. from 19.95 to 80 wt %, based on the total weight of                the network-forming component, of one or more first                network monomers having a number average of 0.95 to 1.1                polymerizable groups that are able to (co)polymerize                with the polymerizable groups of the TPA-based                polyester, wherein a linear polymer formed from the one                or more first network monomers has a Tg of 40° C. or                more;            -   iii. from 0.05 to 5 wt %, based on the total weight of                the first network-forming component, of one or more                first network initiators capable of initiating the                polymerization of the TPA-based polyester and the first                network monomer; and            -   iv. optionally, up to 15 wt % of one or more further                first network monomers, oligomers, or polymers having a                number average of 2 or more polymerizable groups that                are able to (co)polymerize with the polymerizable groups                of the TPA-based polyester or the one or more                first-network monomers;        -   b. optionally, a second network-forming component comprising            one or more second network compounds comprising            polymerizable groups that do not (co)polymerize with the            polymerizable groups of the TPA-based polyester, and a            second network initiator for initiating the polymerization            of the one or more second network compounds; and        -   c. optionally, a particulate filler comprising a            polymerizable group that is able to (co)polymerize with the            polymerizable groups of the TPA-based polyester.    -   2) A kit of materials comprising a particulate sub-composition        and a liquid sub-composition, which when combined forms a        composition for forming an object by an additive fabrication        process that comprises a first-network forming component        comprising polymerizable groups, and optionally a second        network-forming component that does not (co)polymerize with the        polymerizable groups of the first-network forming component, the        kit comprising:        -   a. a particulate sub-composition comprising:            -   i. from 19.95 to 80 wt %, based on the total weight of                the first network-forming component, of a TPA-based                polyester comprising a backbone and having a number                average of at least 2 polymerizable groups, wherein the                backbone comprises the reaction product of a                terephthalic acid and a polyol, wherein the                polymerizable groups comprise acrylate, methacrylate,                epoxy, oxetane, hydroxyl, itaconate, vinyl ether, allyl                ether, maleate, or fumarate, and wherein the TPA-based                polyester has a number average molecular weight of from                800 to 10000 g/mol and a Tg of 40° C. or more;            -   ii. optionally, a particulate filler comprising a                polymerizable group that is able to (co)polymerize with                the polymerizable groups of the TPA-based polyester;        -   b. a liquid sub-composition comprising:            -   i. from 19.95 to 80 wt %, based on the total weight of                the network-forming component, of one or more first                network monomers having a number average of 0.95 to 1.1                polymerizable groups that are able to (co)polymerize                with the polymerizable groups of the TPA-based                polyester, wherein a linear polymer formed from the one                or more first network monomers has a Tg of 40° C. or                more;            -   ii. optionally, up to 15 wt % of one or more further                first network monomers, oligomers, or polymers having a                number average of 2 or more polymerizable groups that                are able to (co)polymerize with the polymerizable groups                of the TPA-based polyester or the one or more                first-network monomers;        -   c. from 0.05 to 5 wt %, based on the total weight of the            first network-forming component, of one or more first            network initiators capable of initiating the polymerization            of the TPA-based polyester and the first network monomer,            wherein the one or more first network initiators may be            present in the particulate sub-composition, the liquid            sub-composition, or both; and        -   d. optionally, a second network-forming component comprising            one or more second network compounds comprising            polymerizable groups that do not (co)polymerize with the            polymerizable groups of the TPA-based polyester, and a            second network initiator for initiating the polymerization            of the one or more second network compounds, wherein the            substituents of the second network-forming component may be            present in the particulate sub-composition, the liquid            sub-composition, or partially in the particulate            sub-composition and partially in the liquid sub-composition.    -   3) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the first network-forming        component consists of the TPA-based polyester, the one or more        first network monomers, the one or more first network        initiators, and, optionally, up to 15 wt % of the further first        network monomer, oligomer, or polymer.    -   4) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the first network-forming        component consists of the TPA-based polyester, the one or more        first network monomers, and the one or more first network        initiators.    -   5) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester is        soluble in the one or more first network monomers.    -   6) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the first network-forming        component is present in an amount of 20 wt % or more, 25 wt % or        more, 30 wt % or more, 35 wt % or more, 40 wt % or more, 50 wt %        or more, 60 wt % or more, 70 wt % or more, 80 wt % or more, 90        wt % or more, 95 wt % or more, or 100 wt %, based on the total        weight of the composition.    -   7) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the first network-forming        component is present in an amount of 100 wt % or less, 90 wt %        or less, 80 wt % or less, 70 wt % or less, or 60 wt % or less,        based on the total weight of the composition.    -   8) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the first network-forming        component is present in an amount of 20 wt % or more, 25 wt % or        more, 30 wt % or more, 35 wt % or more, 40 wt % or more, 50 wt %        or more, 60 wt % or more, 70 wt % or more, 80 wt % or more, 90        wt % or more, 95 wt % or more, or 100 wt %, based on the total        weight of the composition, excluding the weight of any solvent.    -   9) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the first network-forming        component is present in an amount of 100 wt % or less, 90 wt %        or less, 80 wt % or less, 70 wt % or less, or 60 wt % or less,        based on the total weight of the composition, excluding the        weight of any solvent.    -   10) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the first network-forming        component is present in an amount of 20 wt % or more, 25 wt % or        more, 30 wt % or more, 35 wt % or more, 40 wt % or more, 50 wt %        or more, 60 wt % or more, 70 wt % or more, 80 wt % or more, 90        wt % or more, 95 wt % or more, or 100 wt %, based on the total        weight of the composition excluding the weight of any solvent        and the weight of any components that do not comprise a        polymerizable group (e.g. a non-reactive particulate filler).    -   11) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the first network-forming        component is present in an amount of 100 wt % or less, 90 wt %        or less, 80 wt % or less, 70 wt % or less, or 60 wt % or less,        based on the total weight of the composition excluding the        weight of any solvent and the weight of any components that do        not comprise a polymerizable group (e.g. a non-reactive        particulate filler).    -   12) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the further first network        monomer, oligomer, or polymer is present.    -   13) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester is        linear.    -   14) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester is        branched.    -   15) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the polyol is an aliphatic polyol        or an aromatic polyol.    -   16) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the polyol has at least 2, at        least 3, at least 4, at least 5, or at least 6 hydroxyl groups.    -   17) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the polyol has at most 2, at most        3, at most 4, at most 5, at most 6, at most 8, or at most 10        hydroxyl groups.    -   18) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the Tg of the TPA-based polyester        is at least 45° C., at least 50° C., at least 55° C., at least        60° C., at least 65° C., or at least 70° C.    -   19) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the Tg of the TPA-based polyester        is 150° C. or less, 125° C. or less, or 120° C. or less.    -   20) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the polyol comprises a        polyalkylene polyol.    -   21) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester comprises        a further polyacid other than terephthalic acid.    -   22) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester comprises        a further polyacid other than terephthalic acid, and the further        polyacid comprises phthalic acid or isophthalic acid.    -   23) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester comprises        a further polyacid other than terephthalic acid, and the further        polyacid comprises adipic acid, sebacic acid, phthalic acid,        isophthalic acid, octadecanedioic acid, pimelic acid, suberic        acid, azelaic acid, brassilic acid, dodecanedioic acid, glutaric        acid, maleic acid, fumaric acid, 6-naphthalenedicarboxylic acid,        4,4′-oxybisbenzoic acid, 3,6-dichlorophthalic acid,        tetrachlorophthalic acid, tetrahydrophthalic acid,        hexahydroterephthalic acid,        hexachloroendomethylenetetrahydrophthalic acid,        endomethylenetetrahydrophthalic acid, decanedicarboxylic acid,        succinic acid, or trimellitic acid.    -   24) The composition or kit according to any one of the preceding        exemplary embodiments, wherein at least 20 mol %, at least 30        mol %, at least 40 mol %, at least 50 mol %, at least 60 mol %,        at least 70 mol %, at least 75 mol %, at least 80 mol %, at        least 85 mol %, at least 90 mol %, at least 95 mol %, at least        98 mol %, or 100 mol % of the backbone of the TPA-based        polyester comprises the reaction product of a polyacid and a        polyol.    -   25) The composition or kit according to any one of the preceding        exemplary embodiments, wherein at most 100 mol %, at most 98 mol        %, at most 95 mol %, at most 90 mol %, at most 80 mol %, at most        70 mol %, or at most 60 mol % of the backbone of the TPA-based        polyester comprises the reaction product of a polyacid and a        polyol.    -   26) The composition or kit according to any one of the preceding        exemplary embodiments, wherein at least 20 mol %, at least 30        mol %, at least 40 mol %, at least 50 mol %, at least 60 mol %,        at least 70 mol %, at least 75 mol %, at least 80 mol %, at        least 85 mol %, at least 90 mol %, at least 95 mol %, at least        98 mol %, or 100 mol % of the backbone of the TPA-based        polyester comprises the reaction product of a TPA and a polyol.    -   27) The composition or kit according to any one of the preceding        exemplary embodiments, wherein at most 100 mol %, at most 98 mol        %, at most 95 mol %, at most 90 mol %, at most 80 mol %, at most        70 mol %, or at most 60 mol % of the backbone of the TPA-based        polyester comprises the reaction product of a TPA and a polyol.    -   28) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester has a        number average of at least 2 polymerizable groups, wherein the        polymerizable groups comprise acrylate, methacrylate, hydroxyl,        epoxy, oxetane, or itaconate.    -   29) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester has a        number average of at least 2 polymerizable groups, wherein the        polymerizable groups consist of acrylate, methacrylate,        hydroxyl, epoxy, oxetane, or itaconate.    -   30) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester has a        number average of at least 2 polymerizable groups, wherein the        polymerizable groups comprise acrylate, methacrylate, epoxy, or        oxetane.    -   31) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester has a        number average of at least 2 polymerizable groups, wherein the        polymerizable groups consist of acrylate, methacrylate, epoxy,        or oxetane.    -   32) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester has a        number average of at least 2 polymerizable groups, wherein the        polymerizable groups comprise acrylate, methacrylate, or epoxy.    -   33) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester has a        number average of at least 2 polymerizable groups, wherein the        polymerizable groups consist of acrylate, methacrylate, or        epoxy.    -   34) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester has a        number average of at least 2 polymerizable groups, wherein the        polymerizable groups comprise acrylate or methacrylate.    -   35) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester has a        number average of at least 2 polymerizable groups, wherein the        polymerizable groups consist of acrylate or methacrylate.    -   36) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester has a        number average of at least 2 polymerizable groups, wherein the        polymerizable groups comprise methacrylate.    -   37) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester has a        number average of at least 2 polymerizable groups, wherein the        polymerizable groups consist of methacrylate.    -   38) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester has a        number average of at least 2 polymerizable groups, wherein the        polymerizable groups comprise endgroups.    -   39) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester has a        number average of at least 2 polymerizable groups, wherein the        polymerizable groups consist of endgroups.    -   40) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester has a        number average of at least 2 polymerizable groups, wherein the        polymerizable groups consist of endgroups and there are no        polymerizable groups that are not endgroups in the TPA-based        polyester.    -   41) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester has a        number average of at least 2.0, at least 2.1, at least 2.2, at        least 2.3, at least 2.4, at least 2.5, at least 2.6, or at least        2.7 polymerizable groups per molecule.    -   42) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester has a        number average of at most 10, at most 9, at most 8, at most 7,        at most 6, at most 5, at most 4.5, at most 4, at most 3.5, or at        most 3 polymerizable groups per molecule.    -   43) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester has a        number average molecular weight of at least 800 g/mol, at least        900 g/mol, at least 1000 g/mol, at least 1100 g/mol, at least        1200 g/mol, at least 1300 g/mol, at least 1400 g/mol, or at        least 1500 g/mol.    -   44) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester has a        number average molecular weight of at most 10,000 g/mol, at most        9,000 g/mol, at most 8,000 g/mol, at most 7000 g/mol, at most        6,000 g/mol, at most 5,000 g/mol, at most 4,000 g/mol, or at        most 3,000 g/mol.    -   45) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester has a        number average of from 2 to 3 polymerizable groups, and the        amount, number average molecular weight, and number average of        polymerizable groups of the TPA-based polyester in the        composition satisfies the following equation:

${X\mspace{11mu} {MPa}} \leq {3*R*T*\left\lbrack {{\left( {3 - f} \right)*\left( \frac{\rho*w_{polyester}}{M_{polyester}} \right)} + {\left( {f - 2} \right)*3*\left( \frac{\rho*w_{polyester}}{M_{polyester}} \right)}} \right\rbrack} \leq {Y\mspace{11mu} {MPa}}$

-   -   -   wherein R is the gas constant 8.314 cm³ MPa K⁻¹ mol⁻¹, T is            423.15 K, f is the number average of polymerizable groups of            the TPA-based polyester, ρ is the density of the TPA-based            polyester in g/cm³, M_(polyester) is the number average            molecular weight of the TPA-based polyester in g/mol, and            w_(polyester) is the weight fraction of the TPA-based            polyester in the first network-forming component, X is 3,            and Y is 50.

    -   46) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester has a        number average of from 2 to 3 polymerizable groups, and the        amount, number average molecular weight, and number average of        polymerizable groups of the TPA-based polyester in the        composition satisfies the following equation:

${{X\mspace{11mu} {MPa}} \leq {3*R*T*\left\lbrack {{\left( {3 - f} \right)*\left( \frac{\rho*w_{polyester}}{M_{polyester}} \right)} + {\left( {f - 2} \right)*3*\left( \frac{\rho*w_{polyester}}{M_{polyester}} \right)}} \right\rbrack} \leq {Y\; {MPa}}}\;$

-   -   -   wherein R is the gas constant 8.314 cm³ MPa K⁻¹ mol⁻¹, T is            423.15 K, f is the number average of polymerizable groups of            the TPA-based polyester, ρ is the density of the TPA-based            polyester in g/cm³, M_(polyester) is the number average            fraction of the TPA-based polyester in the first            network-forming component, X is 3, 5, 7, 10, 15 or 20, and Y            is 50, 45, or 40.

    -   47) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester is        present in an amount of at least 5 wt %, at least 10 wt %, at        least 15 wt %, at least 19.95 wt %, at least 20 wt %, at least        25 wt %, at least 30 wt %, at least 40 wt %, at least 50 wt %,        at least 60 wt %, at least 70 wt %, or at least 80 wt %, based        on the total weight of the composition.

    -   48) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester is        present in an amount of at most 80 wt %, at most 78 wt %, at        most 75 wt %, at most 70 wt %, at most 60 wt %, at most 50 wt %,        at most 40 wt %, at most 30 wt %, or at most 20 wt %, based on        the total weight of the composition.

    -   49) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester is        present in an amount of at least 5 wt %, at least 10 wt %, at        least 15 wt %, at least 19.95 wt %, at least 20 wt %, at least        25 wt %, at least 30 wt %, at least 40 wt %, at least 50 wt %,        at least 60 wt %, at least 70 wt %, or at least 80 wt %, based        on the total weight of the composition excluding any solvent.

    -   50) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester is        present in an amount of at most 80 wt %, at most 78 wt %, at        most 75 wt %, at most 70 wt %, at most 60 wt %, at most 50 wt %,        at most 40 wt %, at most 30 wt %, or at most 20 wt %, based on        the total weight of the composition excluding any solvent.

    -   51) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester is        present in an amount of at least 19.95 wt %, at least 20 wt %,        at least 25 wt %, at least 30 wt %, at least 40 wt %, at least        50 wt %, at least 60 wt %, at least 70 wt %, or at least 80 wt        %, based on the total weight of the first network-forming        component.

    -   52) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester is        present in an amount of at most 80 wt %, at most 78 wt %, at        most 75 wt %, at most 70 wt %, at most 60 wt %, at most 50 wt %,        at most 40 wt %, at most 30 wt %, or at most 20 wt %, based on        the total weight of the first network-forming component.

    -   53) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester comprises        a polymerizable group comprising acrylate, methacrylate,        itaconate, allyl ether, maleate, or fumarate and the first        network monomer and optional further first network monomer,        oligomer, or polymer are free radically polymerizable compounds        and the first network initiator is a free-radical initiator.

    -   54) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester comprises        a polymerizable group comprising hydroxyl, epoxy, or oxetane and        the first network monomer and optional further first network        monomer, oligomer, or polymer are cationically polymerizable        compounds and the first network initiator is a cationic        initiator.

    -   55) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester comprises        a number average of at least 2 acrylate, methacrylate,        itaconate, allyl ether, maleate, or fumarate groups per        molecule, the one or more first network monomers comprise an        acrylate, methacrylate, itaconate, vinyl ether, allyl ether,        maleate, or fumarate group and the optional further first        network monomer, oligomer or polymer comprises a number average        of 2 or more acrylate, methacrylate, itaconate, vinyl ether,        allyl ether, maleate, or fumarate groups.

    -   56) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester comprises        a number average of at least 2 hydroxyl, epoxy, or oxetane        groups per molecule, the one or more first network monomers        comprise a hydroxyl, epoxy, oxetane, or vinyl ether group and        the optional further first network monomer, oligomer or polymer        comprises a number average of 2 or more hydroxyl, epoxy,        oxetane, or vinyl ether groups.

    -   57) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester comprises        a number average of at least 2 vinyl ether groups per molecule,        the one or more first network monomers comprise an acrylate,        methacrylate, itaconate, hydroxyl, epoxy, oxetane, vinyl ether,        allyl ether, maleate, or fumarate group and the optional further        first network monomer, oligomer or polymer comprises a number        average of 2 or more acrylate, methacrylate, itaconate,        hydroxyl, epoxy, oxetane, vinyl ether, allyl ether, maleate, or        fumarate groups.

    -   58) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the first network initiator is a        free-radical photo-initiator.

    -   59) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the first network initiator is a        cationic photo-initiator.

    -   60) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester is        amorphous.

    -   61) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester comprises        a blend of amorphous and semi-crystalline TPA-based polyesters.

    -   62) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester comprises        a blend of amorphous, semi-crystalline, and crystalline        TPA-based polyesters.

    -   63) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester comprises        a blend of at least two different TPA-based polyesters, wherein        a first TPA-based polyester has a number average of more than        three polymerizable groups per molecule, wherein a second        TPA-based polyester has a number average of less than three        polymerizable groups per molecule, and wherein the number        average polymerizable groups per molecule of the TPA-based        polyester is from two to three polymerizable groups per        molecule.

    -   64) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester comprises        at least one acrylate group and at least one methacrylate group.

    -   65) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester        comprises i) at least one acrylate or methacrylate group,        and ii) at least one epoxy group, the one or more first network        monomers comprise an acrylate, methacrylate, itaconate,        hydroxyl, epoxy, oxetane, vinyl ether, allyl ether, maleate, or        fumarate group and the optional further first network monomer,        oligomer or polymer comprises a number average of 2 or more        acrylate, methacrylate, itaconate, hydroxyl, epoxy, oxetane,        vinyl ether, allyl ether, maleate, or fumarate groups.

    -   66) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester        comprises i) at least one polymerizable group selected from        acrylate, methacrylate, itaconate, allyl ether, maleate, or        fumarate, and ii) at least one polymerizable group selected from        hydroxyl, epoxy, or oxetane, the one or more first network        monomers comprise an acrylate, methacrylate, itaconate,        hydroxyl, epoxy, oxetane, vinyl ether, allyl ether, maleate, or        fumarate group and the optional further first network monomer,        oligomer or polymer comprises a number average of 2 or more        acrylate, methacrylate, itaconate, hydroxyl, epoxy, oxetane,        vinyl ether, allyl ether, maleate, or fumarate groups.

    -   67) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the first network monomer has a        number average of 0.95 polymerizable groups or more, 0.97        polymerizable groups or more, or 0.99 polymerizable groups or        more.

    -   68) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the first network monomer has a        number average of 1.1 polymerizable groups or less, 1.08        polymerizable groups or less, 1.06 polymerizable groups or less,        1.04 polymerizable groups or less, or 1.02 polymerizable groups        or less. In an embodiment, the first network monomer has a        number average of 1.0 polymerizable groups.

    -   69) The composition or kit according to any one of the preceding        exemplary embodiments, wherein a linear polymer formed from the        one or more first network monomers has a Tg of 50° C. or more,        60° C. or more, 65° C. or more, 70° C. or more, 75° C. or more,        80° C. or more, 85° C. or more, 90° C. or more, 95° C. or more,        or 100° C. or more.

    -   70) The composition or kit according to any one of the preceding        exemplary embodiments, wherein a linear polymer formed from the        one or more first network monomers has a Tg of 150° C. or less,        130° C. or less, 125° C. or less, or 120° C. or less.

    -   71) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the one or more first network        monomers has a molecular weight of 800 g/mol or less, 700 g/mol        or less, 600 g/mol or less, 500 g/mol or less, 400 g/mol or        less, 350 g/mol or less, 300 g/mol or less, 250 g/mol or less,        or 200 g/mol or less.

    -   72) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the one or more first network        monomers has a molecular weight of 100 g/mol or more, or 150        g/mol or more.

    -   73) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester comprises        a polymerizable group comprising acrylate, methacrylate,        itaconate, vinyl ether, allyl ether, maleate, or fumarate and        the first network monomer comprises methyl (meth)acrylate,        hydroxy ethyl (meth)acrylate, ethyl (meth)acrylate, propyl        (meth)acrylate, isopropyl (meth)acrylate, isobutyl        (meth)acrylate, t-butyl (meth)acrylate, hydroxy propyl        (meth)acrylate, cyclohexyl (meth)acrylate, benzyl        (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate,        isobutyl (meth)acrylate, acryloyl morpholine, dimethyl        itaconate, N-vinyl pyrollidone, N-vinyl caprolactam, N-vinyl        imidazole, or N-methyl-N-vinylacetamide.

    -   74) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester comprises        a polymerizable group comprising acrylate, methacrylate,        itaconate, vinyl ether, allyl ether, maleate, or fumarate and        the first network monomer comprises cyclohexyl vinyl ether,        1,4,-cyclohexanedimethanol mono vinyl ether, tert-Butyl vinyl        ether, phenyl vinyl ether, allyl phenyl ether, dimethyl maleate,        diethyl maleate, dimethyl fumarate, or diethyl fumarate.

    -   75) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the TPA-based polyester comprises        a polymerizable group comprising hydroxyl, epoxy, oxetane, or        vinyl ether and the one or more first network monomers comprise        cyclohexene oxide, tert-butyl glycidyl ether, 4-chlorophenyl        glycidyl ether, cyclopentene oxide, exo-2,3-Epoxynorbornane,        1,2-Epoxy-3-phenoxypropane, (2,3-Epoxypropyl)benzene,        N-(2,3-Epoxypropyl)phthalimide,        exo-3,6-Epoxy-1,2,3,6-tetrahydrophthalic anhydride,        3,4-Epoxytetrahydrothiophene-1,1-dioxide, Furfuryl glycidyl        ether, glycidyl 4-methoxyphenyl ether, glycidyl 2-methylphenyl        ether, isophorone oxide, α-Pinene oxide, cis-stilbene oxide,        styrene oxide, Methyl 7-oxabicyclo[4.1.0]heptane-3-carboxylate,        2-Ethylhexyl 7-oxabicyclo(4.1.0)heptane-3-carboxylate,        3-ethyl-3-hydroxymethyloxetane,        3-ethyl-3-(3-hydroxypropyl)oxymethyloxetane,        3-ethyl-3-(4-hydroxybutyl)oxymethyloxetane, cyclohexyl vinyl        ether, 1,4,-cyclohexanedimethanol mono vinyl ether, tert-Butyl        vinyl ether, or phenyl vinyl ether.

    -   76) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the one or more first network        monomers are present in an amount of at least 10 wt %, at least        15 wt %, at least 19.95 wt %, at least 20 wt %, at least 25 wt        %, at least 30 wt %, at least 40 wt %, at least 50 wt %, at        least 60 wt %, at least 70 wt %, or at least 80 wt %, based on        the total weight of the composition.

    -   77) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the one or more first network        monomers are present in an amount of at most 80 wt %, at most 78        wt %, at most 75 wt %, at most 70 wt %, at most 60 wt %, at most        50 wt %, at most 40 wt %, at most 30 wt %, or at most 20 wt %,        based on the total weight of the composition.

    -   78) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the one or more first network        monomers are present in an amount of at least 10 wt %, at least        15 wt %, at least 19.95 wt %, at least 20 wt %, at least 25 wt        %, at least 30 wt %, at least 40 wt %, at least 50 wt %, at        least 60 wt %, at least 70 wt %, or at least 80 wt %, based on        the total weight of the composition excluding any solvent.

    -   79) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the one or more first network        monomers are present in an amount of at most 80 wt %, at most 78        wt %, at most 75 wt %, at most 70 wt %, at most 60 wt %, at most        50 wt %, at most 40 wt %, at most 30 wt %, or at most 20 wt %,        based on the total weight of the composition excluding any        solvent.

    -   80) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the one or more first network        monomers are present in an amount of at least 19.95 wt %, at        least 20 wt %, at least 25 wt %, at least 30 wt %, at least 40        wt %, at least 50 wt %, at least 60 wt %, at least 70 wt %, or        at least 80 wt %, based on the total weight of the first        network-forming component.

    -   81) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the one or more first network        monomers are present in an amount of at most 80 wt %, at most 78        wt %, at most 75 wt %, at most 70 wt %, at most 60 wt %, at most        50 wt %, at most 40 wt %, at most 30 wt %, or at most 20 wt %,        based on the total weight of the first network-forming        component.

    -   82) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the one or more first network        initiators comprise a photo-initiator or a thermal initiator.

    -   83) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the one or more first network        initiators comprise a photo-initiator that initiates        polymerization in response to UV light, visible light, or both        UV light and visible light.

    -   84) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the one or more first network        initiators comprise a photo-initiator that initiates        polymerization at a wavelength of from 300 to 470 nm.

    -   85) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the one or more first network        initiators comprise a photo-initiator that initiates        polymerization at a wavelength of from 300 to 395 nm.

    -   86) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the one or more first network        initiators comprise a photo-initiator and a thermal initiator.

    -   87) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the one or more first network        initiators comprise a thermal initiator.

    -   88) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the one or more first network        initiators are present in an amount of at least 0.01 wt %, at        least 0.05 wt %, at least 0.1 wt %, at least 0.2 wt %, at least        0.3 wt %, at least 0.4 wt %, at least 0.5 wt %, at least 1.0 wt        %, at least 1.5 wt %, at least 2 wt %, or at least 2.5 wt %,        based on the total weight of the composition.

    -   89) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the one or more first network        monomers are present in an amount of at most 10 wt %, at most 8        wt %, at most 7 wt %, at most 6 wt %, at most 5 wt %, or at most        4 wt %, based on the total weight of the composition.

    -   90) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the one or more first network        initiators are present in an amount of at least 0.01 wt %, at        least 0.05 wt %, at least 0.1 wt %, at least 0.2 wt %, at least        0.3 wt %, at least 0.4 wt %, at least 0.5 wt %, at least 1.0 wt        %, at least 1.5 wt %, at least 2 wt %, or at least 2.5 wt %,        based on the total weight of the composition excluding any        solvent.

    -   91) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the one or more first network        monomers are present in an amount of at most 10 wt %, at most 8        wt %, at most 7 wt %, at most 6 wt %, at most 5 wt %, or at most        4 wt %, based on the total weight of the composition excluding        any solvent.

    -   92) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the one or more first network        initiators are present in an amount of at least 0.01 wt %, at        least 0.05 wt %, at least 0.1 wt %, at least 0.2 wt %, at least        0.3 wt %, at least 0.4 wt %, at least 0.5 wt %, at least 1.0 wt        %, at least 1.5 wt %, at least 2 wt %, or at least 2.5 wt %,        based on the total weight of the first network-forming        component.

    -   93) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the one or more first network        initiators are present in an amount of at most 10 wt %, at most        8 wt %, at most 7 wt %, at most 6 wt %, at most 5 wt %, or at        most 4 wt %, based on the total weight of the first        network-forming component.

    -   94) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the further first network        monomer, oligomer, or polymer is present in an amount of at most        15 wt %, at most 12 wt %, at most 10 wt %, at most 8 wt %, at        most 6 wt %, at most 5 wt %, at most 4 wt %, at most 3 wt %, or        at most 2 wt %, based on the total weight of the composition.

    -   95) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the further first network        monomer, oligomer, or polymer is present in an amount of at        least 0.5 wt %, at least 1 wt %, at least 1.5 wt %, at least 2        wt %, at least 2.5 wt %, at least 4 wt %, or at least 5 wt %,        based on the total weight of the composition.

    -   96) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the further first network        monomer, oligomer, or polymer is present in an amount of at most        15 wt %, at most 12 wt %, at most 10 wt %, at most 8 wt %, at        most 6 wt %, at most 5 wt %, at most 4 wt %, at most 3 wt %, or        at most 2 wt %, based on the total weight of the composition        excluding any solvent.

    -   97) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the further first network        monomer, oligomer, or polymer is present in an amount of at        least 0.5 wt %, at least 1 wt %, at least 1.5 wt %, at least 2        wt %, at least 2.5 wt %, at least 4 wt %, or at least 5 wt %,        based on the total weight of the composition excluding any        solvent.

    -   98) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the further first network        monomer, oligomer, or polymer is present in an amount of at most        15 wt %, at most 12 wt %, at most 10 wt %, at most 8 wt %, at        most 6 wt %, at most 5 wt %, at most 4 wt %, at most 3 wt %, or        at most 2 wt %, based on the total weight of the first        network-forming component.

    -   99) The composition or kit according to any one of the preceding        exemplary embodiments, wherein the further first network        monomer, oligomer, or polymer is present in an amount of at        least 0.5 wt %, at least 1 wt %, at least 1.5 wt %, at least 2        wt %, at least 2.5 wt %, at least 4 wt %, or at least 5 wt %,        based on the total weight of the first network-forming        component.

    -   100) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the TPA-based polyester        comprises polymerizable groups comprising acrylate,        methacrylate, or itaconate, and the one or more second network        compounds comprises polymerizable groups that comprise epoxy,        oxetane, or hydroxyl.

    -   101) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the TPA-based polyester        comprises polymerizable groups comprising epoxy, oxetane, or        hydroxyl, and the one or more second network compounds comprises        polymerizable groups that comprise acrylate, methacrylate, or        itaconate.

    -   102) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the second        network-forming component is present in an amount of 5 wt % or        more, 10 wt % or more, 15 wt % or more, 20 wt % or more, 25 wt %        or more, 30 wt % or more, 35 wt % or more, 40 wt % or more, 50        wt % or more, 60 wt % or more, or 70 wt % or more, based on the        total weight of the composition.

    -   103) The composition or kit according to any one of the        preceding exemplary embodiments, wherein second network-forming        component is present in an amount of 90 wt % or less, 80 wt % or        less, 70 wt % or less, 60 wt % or less, 50 wt % or less, 40 wt %        or less, 30 wt % or less, or 20 wt % or less, based on the total        weight of the composition.

    -   104) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the composition is        devoid of second network-forming component.

    -   105) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the composition is        substantially devoid of second network-forming component.

    -   106) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the second        network-forming component is present in an amount of 5 wt % or        more, 10 wt % or more, 15 wt % or more, 20 wt % or more, 25 wt %        or more, 30 wt % or more, 35 wt % or more, 40 wt % or more, 50        wt % or more, 60 wt % or more, or 70 wt % or more, based on the        total weight of the composition, excluding the weight of any        solvent.

    -   107) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the second        network-forming component is present in an amount of 90 wt % or        less, 80 wt % or less, 70 wt % or less, 60 wt % or less, 50 wt %        or less, 40 wt % or less, 30 wt % or less, or 20 wt % or less,        based on the total weight of the composition excluding any        solvent.

    -   108) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the second        network-forming component is present in an amount of 5 wt % or        more, 10 wt % or more, 15 wt % or more, 20 wt % or more, 25 wt %        or more, 30 wt % or more, 35 wt % or more, 40 wt % or more, 50        wt % or more, 60 wt % or more, or 70 wt % or more, based on the        total weight of the composition excluding any solvent and any        components that do not comprise a polymerizable group.

    -   109) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the second        network-forming component is present in an amount of 90 wt % or        less, 80 wt % or less, 70 wt % or less, 60 wt % or less, 50 wt %        or less, 40 wt % or less, 30 wt % or less, or 20 wt % or less,        based on the total weight of the composition excluding any        solvent and any components that do not comprise a polymerizable        group.

    -   110) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the one or more second        network compounds are present in an amount of at least 5 wt %,        at least 10 wt %, at least 15 wt %, at least 19.95 wt %, at        least 20 wt %, at least 25 wt %, at least 30 wt %, at least 40        wt %, at least 50 wt %, at least 60 wt %, at least 70 wt %, or        at least 80 wt %, based on the total weight of the composition.

    -   111) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the one or more second        network compounds are present in an amount of at most 80 wt %,        at most 78 wt %, at most 75 wt %, at most 70 wt %, at most 60 wt        %, at most 50 wt %, at most 40 wt %, at most 30 wt %, or at most        20 wt %, based on the total weight of the composition.

    -   112) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the one or more second        network compounds are present in an amount of at least 5 wt %,        at least 10 wt %, at least 15 wt %, at least 19.95 wt %, at        least 20 wt %, at least 25 wt %, at least 30 wt %, at least 40        wt %, at least 50 wt %, at least 60 wt %, at least 70 wt %, or        at least 80 wt %, based on the total weight of the composition        excluding any solvent.

    -   113) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the one or more second        network compounds are present in an amount of at most 80 wt %,        at most 78 wt %, at most 75 wt %, at most 70 wt %, at most 60 wt        %, at most 50 wt %, at most 40 wt %, at most 30 wt %, or at most        20 wt %, based on the total weight of the composition excluding        any solvent.

    -   114) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the one or more second        network compounds are present in an amount of at least 50 wt %,        at least 60 wt %, at least 70 wt %, at least 80 wt %, or at        least 90 wt %, based on the total weight of the second        network-forming component.

    -   115) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the one or more second        network compounds are present in an amount of at most 99.9 wt %,        at most 99.5 wt %, at most 99 wt %, at most 98 wt %, at most 97        wt %, at most 96 wt %, at most 95 wt %, at most 90 wt %, or at        most 80 wt %, based on the total weight of the second        network-forming component.

    -   116) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the second network        initiator comprises a photo-initiator or a thermal initiator.

    -   117) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the second network        initiator comprises a photo-initiator that initiates        polymerization in response to UV light, visible light, or both        UV light and visible light.

    -   118) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the second network        initiator comprises a photo-initiator and a thermal initiator.

    -   119) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the second network        initiator is present in an amount at least 0.01 wt %, at least        0.05 wt %, at least 0.1 wt %, at least 0.2 wt %, at least 0.3 wt        %, at least 0.4 wt %, at least 0.5 wt %, at least 1.0 wt %, at        least 1.5 wt %, at least 2 wt %, or at least 2.5 wt %, based on        the total weight of the composition excluding any solvent.

    -   120) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the second network        initiator is present in an amount of at most 10 wt %, at most 8        wt %, at most 7 wt %, at most 6 wt %, at most 5 wt %, or at most        4 wt %, based on the total weight of the composition excluding        any solvent.

    -   121) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the second network        initiator is present in an amount of at least 0.01 wt %, at        least 0.05 wt %, at least 0.1 wt %, at least 0.2 wt %, at least        0.3 wt %, at least 0.4 wt %, at least 0.5 wt %, at least 1.0 wt        %, at least 1.5 wt %, at least 2 wt %, or at least 2.5 wt %,        based on the total weight of the second network-forming        component.

    -   122) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the second network        initiator is present in an amount of at most 10 wt %, at most 8        wt %, at most 7 wt %, at most 6 wt %, at most 5 wt %, or at most        4 wt %, based on the total weight of the second network-forming        component.

    -   123) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the composition further        comprises an organic or inorganic particulate filler, such as        SiO₂, AlO₂, TiO₂, ZnO₂, SnO₂, Am—SnO₂, ZrO₂, Sb—SnO₂, Al₂O₃, or        carbon black.

    -   124) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the composition further        comprises a particulate filler comprising a polymerizable group        that is able to (co)polymerize with the polymerizable groups of        the TPA-based polyester.

    -   125) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the particulate filler        comprises a polymerizable group that is able to (co)polymerize        with the polymerizable groups of the one or more second network        compounds.

    -   126) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the particulate filler        comprises a polymerizable group comprising acrylate,        methacrylate, epoxy, oxetane, hydroxyl, itaconate, vinyl ether,        allyl ether, maleate, or fumarate.

    -   127) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the particulate filler        comprises a polymerizable group comprising acrylate,        methacrylate, epoxy, oxetane, hydroxyl, or itaconate.

    -   128) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the particulate filler        comprises a polymerizable group comprising acrylate or        methacrylate.

    -   129) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the particulate filler        comprises a polymerizable group comprising epoxy, oxetane or        hydroxyl.

    -   130) The composition or kit according to any one of the        preceding exemplary embodiments, wherein particulate filler        comprises an impact modifier.

    -   131) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the particulate filler        is present in the composition in an amount of 1 wt % or more, 5        wt % or more, 10 wt % or more, 15 wt % or more, 20 wt % or more,        30 wt % or more, 40 wt % or more, or 50 wt % or more, based on        the total weight of the composition.

    -   132) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the particulate filler        is present in the composition in an amount of 90 wt % or less,        80 wt % or less, 70 wt % or less, 60 wt % or less, 50 wt % or        less, 40 wt % or less, 30 wt % or less, or 20 wt % or less,        based on the total weight of the composition.

    -   133) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the composition further        comprises a stabilizer, such as a viscosity stabilizer or light        stabilizer, a UV absorber, a dye, a pigment, a plasticizer, a        surfactant, an antioxidant, a wetting agent, a photosensitizer,        a defoamer, a flame retardant, a silane coupling agent, an acid        scavenger, an accelerators for a thermal initiator, and/or a        bubble breaker.

    -   134) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the composition further        comprises a non-particulate impact modifier.

    -   135) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the composition further        comprises a non-particulate impact modifier and the        non-particulate impact modifier does not comprise a        polymerizable group.

    -   136) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the composition further        comprises a non-particulate impact modifier and the        non-particulate impact modifier comprises a polymerizable group.

    -   137) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the non-particulate        impact modifier comprises a block copolymer.

    -   138) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the further first        network monomer, oligomer, or polymer comprises a        non-particulate impact modifier comprising a polymerizable        group.

    -   139) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the second network        compound comprises a non-particulate impact modifier comprising        a polymerizable group.

    -   140) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the composition        comprises 50 wt % or less of solvent, based on the total weight        of the composition, wt % or less, 30 wt % or less, 20 wt % or        less, 10 wt % or less, 5 wt % or less, or 0 wt %.

    -   141) The composition or kit according to any one of the        preceding exemplary embodiments, the viscosity of the        composition at 30° C. is 4000 cps or less, 3000 cps, or less,        2000 cps or less, 1500 cps or less, or 1200 cps or less.

    -   142) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the viscosity of the        composition at 30° C. is 300 cps or more.

    -   143) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the composition or        liquid sub-composition further comprises a dispersing medium.

    -   144) The composition according to any one of the preceding        exemplary embodiments, wherein the composition further comprises        from 20 to 70 wt % of a dispersing medium.

    -   145) The kit according to any one of the preceding exemplary        embodiments, wherein the liquid sub-composition further        comprises from 20 to 80 wt % of a dispersing medium.

    -   146) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the composition or        liquid sub-composition further comprises a dispersing medium and        the dispersing medium comprises water.

    -   147) The composition or kit according to any one of the        preceding exemplary embodiments, wherein the composition or        liquid sub-composition further comprises a dispersing medium and        the dispersing medium consists of water.

    -   148) An article formed by polymerizing the composition, the        composition optionally formed by combining the elements of the        kit, according to any one of the preceding exemplary        embodiments.

    -   149) An article formed by polymerizing the composition, the        composition optionally formed by combining the elements of the        kit, according to any one of the preceding exemplary        embodiments, wherein a film formed by polymerizing 90% or more        of total the polymerizable groups in the composition has a        tensile modulus as measured at 150° C. of from 3, from 5, from        7, from 10, from 15, or from 20 MPa to 50, to 45, or to 40 MPa,        as determined by DMTA in accordance with ASTM D5026.

    -   150) An article formed by polymerizing the composition, the        composition optionally formed by combining the elements of the        kit, according to any one of the preceding exemplary        embodiments, wherein a film formed by polymerizing 90% or more        of total the polymerizable groups in the composition has a yield        stress at 23° C. of from 50 to 90 MPa, and an elongation at        break at 23° C. of greater than 3%, as determined according to        ISO 37:2011.

    -   151) An article formed by polymerizing the composition, the        composition optionally formed by combining the elements of the        kit, according to any one of the preceding exemplary        embodiments, wherein a film formed by polymerizing 90% or more        of total the polymerizable groups in the composition has a        tensile modulus as measured at 23° C. of from 2000 to 3500 MPa,        as determined according to ISO 37:2011.

    -   152) An article formed by polymerizing the composition, the        composition optionally formed by combining the elements of the        kit, according to any one of the preceding exemplary        embodiments, wherein a film formed by polymerizing 90% or more        of total the polymerizable groups has elongation at break at        23° C. of greater than 3% and less than 20%, less than 15%, or        less than 10%.

    -   153) A method of forming a three-dimensional object comprising        the steps of providing a composition according to any one of the        preceding exemplary embodiments, or a composition formed by        combining the elements of the kit according to any one of the        preceding exemplary embodiments, and polymerizing the        composition.

    -   154) A method of forming a three-dimensional object comprising        the steps of forming a layer of the composition according to any        one of the preceding exemplary embodiments, or a composition        formed by combining the elements of the kit according to any one        of the preceding exemplary embodiments, curing the composition        with radiation to form a desired shape, and repeating the steps        of forming and curing a plurality of times to obtain a        three-dimensional object.

    -   155) A method of forming a three-dimensional object comprising        the steps of selectively dispensing the composition according to        any one of the preceding exemplary embodiments, or a composition        formed by combining the elements of the kit according to any one        of the preceding exemplary embodiments, curing the composition        with radiation to form a desired shape, and repeating the steps        of selectively dispensing and curing a plurality of times to        obtain a three-dimensional object.

    -   156) A method of forming a three-dimensional object comprises        the steps of forming a layer of the composition according to any        one of the preceding exemplary embodiments, or a composition        formed by combining the elements of the kit according to any one        of the preceding exemplary embodiments, selectively curing the        layer with radiation to form a desired shape, and repeating the        steps of forming and selectively curing a layer of the        composition a plurality of times to obtain a three-dimensional        object.

    -   157) A method of forming a three-dimensional article by        polymerizing the composition according to any one of the        preceding exemplary embodiments, or by polymerizing a        composition formed by combining the elements of the kit        according to any one of the preceding exemplary embodiments, the        method comprising the steps of forming a layer from a first        composition comprising the TPA-based polyester and selectively        dispensing a second composition comprising one or more first        network monomers onto the first composition in accordance with        the shape of a portion of a three-dimensional object, wherein        the one or more first network initiators are present either in        the layer of TPA-based polyester, in the composition comprising        the one or more first network monomers, or both.

    -   158) A method of forming a three-dimensional article from the        kit of any one of the preceding exemplary embodiments,        comprising the steps of forming a layer of the particulate        sub-composition; selectively dispensing, such as by jetting, or        non-selectively dispensing the liquid sub-composition;        optionally selectively applying or non-selectively applying        radiation to thereby induce curing of the particulate        sub-composition and liquid sub-composition; and repeating the        steps of forming, dispensing, and selectively curing a plurality        of times in order to form a three-dimensional object.

    -   159) The method according to any one of the preceding exemplary        embodiments, further comprising the step of evaporating the        dispersing medium.

    -   160) The method according to any one of the preceding exemplary        embodiments, wherein the composition is present as a liquid at        the time of curing the composition, such as by initiating the        polymerization reaction by the application of radiation, such as        light or heat.

    -   161) The method according to any one of the preceding exemplary        embodiments, wherein the composition is present as a liquid at        the time of curing the composition, such as by initiating the        polymerization reaction by the application of radiation, such as        light or heat, and wherein the liquid composition possesses a        temperature of 25° or more, 30° C. or more, 35° C. or more,        40° C. or more, or 45° C. or more at the time that        polymerization is initiated.

    -   162) The method according to any one of the preceding exemplary        embodiments, wherein the composition is present as a liquid at        the time of curing the composition, such as by initiating the        polymerization reaction by the application of radiation, such as        light or heat, and wherein the liquid composition possesses a        temperature of 200° C. or less, 180° C. or less, 150° C. or        less, 100° C. or less, 80° C. or less, or 50° C. or less, at the        time that polymerization is initiated.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the invention (especially in the context of thefollowing claims) are to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. The terms “comprising,” “having,” “including,” and “containing”are to be construed as open-ended terms (i.e., meaning “including, butnot limited to”) unless otherwise noted. Recitation of ranges of valuesherein are merely intended to serve as a shorthand method of referringindividually to each separate value falling within the range, unlessotherwise indicated herein, and each separate value is incorporated intothe specification as if it were individually recited herein. The use ofany and all examples, or exemplary language (e.g., “such as”) providedherein, is intended merely to better illuminate the invention and doesnot pose a limitation on the scope of the invention unless otherwiseclaimed. No language in the specification should be construed asindicating any non-claimed element as essential to the practice of theinvention.

Preferred embodiments of this invention are described herein, includingthe best mode known to the inventors for carrying out the invention.Variations of those preferred embodiments may become apparent to thoseof ordinary skill in the art upon reading the foregoing description. Theinventors expect skilled artisans to employ such variations asappropriate, and the inventors intend for the invention to be practicedotherwise than as specifically described herein. Accordingly, thisinvention includes all modifications and equivalents of the subjectmatter recited in the claims appended hereto as permitted by applicablelaw. While certain optional features are described as embodiments of theinvention, the description is meant to encompass and specificallydisclose all combinations of these embodiments unless specificallyindicated otherwise or physically impossible.

1) A composition for forming a three-dimensional object via an additivefabrication process comprising: a. from 30 to 100 wt %, based on thetotal weight of the composition, of a first network-forming componentconsisting of: i. from 19.95 to 80 wt %, based on the total weight ofthe first network-forming component, of a TPA-based polyester comprisinga backbone and having a number average of at least 2 polymerizablegroups, wherein the backbone comprises the reaction product of aterephthalic acid and a polyol, wherein the polymerizable groupscomprise acrylate, methacrylate, epoxy, oxetane, hydroxyl, itaconate,vinyl ether, allyl ether, maleate, or fumarate, and wherein theTPA-based polyester has a number average molecular weight of from 800 to10000 g/mol and a Tg of at least 25° C., or at least 40° C.; ii. from19.95 to 80 wt %, based on the total weight of the network-formingcomponent, of one or more first network monomers having a number averageof 0.95 to 1.1 polymerizable groups that are able to (co)polymerize withthe polymerizable groups of the TPA-based polyester, wherein a linearpolymer formed from the one or more first network monomers has a Tg ofat least 25° C., or at least 40° C.; iii. from 0.05 to 5 wt %, based onthe total weight of the first network-forming component, of one or morefirst network initiators capable of initiating the polymerization of theTPA-based polyester and the first network monomer; and iv. optionally,up to 15 wt % of one or more further first network monomers, oligomers,or polymers having a number average of 2 or more polymerizable groupsthat are able to (co)polymerize with the polymerizable groups of theTPA-based polyester or the one or more first-network monomers; b.optionally, a second network-forming component comprising one or moresecond network compounds comprising polymerizable groups that do not(co)polymerize with the polymerizable groups of the TPA-based polyester,and a second network initiator for initiating the polymerization of theone or more second network compounds; and c. optionally, a particulatefiller comprising a polymerizable group that is able to (co)polymerizewith the polymerizable groups of the TPA-based polyester. 2) Thecomposition of claim 1, wherein the first network initiator comprises aphoto-initiator. 3) The composition of any one of the preceding claims,wherein a film formed by polymerizing 90% or more of total thepolymerizable groups in the composition has a tensile modulus measuredat 150° C. of from 3 and 50 MPa and a Tg of 40° C. or higher. 4) Thecomposition according to any one of the preceding claims, wherein thepolymerizable groups comprise endgroups. 5) The composition according toany one of the preceding claims, wherein the polymerizable groupsconsist of endgroups. 6) The composition of any one of the precedingclaims, wherein the TPA-based polyester has a number average of from 2to 3 endgroups, and wherein the amount, number average molecular weight,and number average of endgroups of the TPA-based polyester in thecomposition satisfies the following equation:${X\mspace{11mu} {MPa}} \leq {3*R*T*\left\lbrack {{\left( {3 - f} \right)*\left( \frac{\rho*w_{polyester}}{M_{polyester}} \right)} + {\left( {f - 2} \right)*3*\left( \frac{\rho*w_{polyester}}{M_{polyester}} \right)}} \right\rbrack} \leq {Y\; {MPa}}$wherein R is the gas constant 8.314 cm³ MPa K⁻¹ mol⁻¹, T is 423.15 K, fis the number average of endgroups of the TPA-based polyester, ρ is thedensity of the TPA-based polyester in g/cm³, M_(polyester) is the numberaverage molecular weight of the TPA-based polyester in g/mol,w_(polyester) is the weight fraction of the TPA-based polyester in thefirst network-forming component, X is 3, and Y is
 50. 7) The compositionof any one of the preceding claims, wherein at least 50 mol % of thebackbone of the TPA-based polyester comprises the reaction product of apolyacid and a polyol, and wherein at least 50 mol % of the polyacidcontent is terephthalic acid. 8) The composition of any one of thepreceding claims, wherein at least 75 mol % of the backbone of theTPA-based polyester comprises the reaction product of a terephthalicacid and a polyol. 9) The composition of any one of the precedingclaims, wherein the TPA-based polyester has a number average of from 2to 3 endgroups. 10) The composition of any one of the preceding claims,wherein the TPA-based polyester has a number average molecular weight offrom 800 to 8000 g/mol. 11) The composition of claim 4, wherein a linearpolymer formed from the one or more first network monomers has a Tg of60° C. or more. 12) The composition of any one of the preceding claims,wherein the one or more first network monomers have a molecular weightof 300 g/mol or less. 13) The composition of any one of the precedingclaims, wherein the one or more first network monomers comprises methyl(meth)acrylate, hydroxy ethyl (meth)acrylate, hydroxy propyl(meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate,isobornyl (meth)acrylate, or isobutyl (meth)acrylate. 14) Thecomposition of any one of the preceding claims, wherein the one or morefirst network monomers comprises cyclohexene oxide, tert-butyl glycidylether, 4-chlorophenyl glycidyl ether, cyclopentene oxide,exo-2,3-Epoxynorbornane, 1,2-Epoxy-3-phenoxypropane,(2,3-Epoxypropyl)benzene, N-(2,3-Epoxypropyl)phthalimide,exo-3,6-Epoxy-1,2,3,6-tetrahydrophthalic anhydride,3,4-Epoxytetrahydrothiophene-1,1-dioxide, Furfuryl glycidyl ether,glycidyl 4-methoxyphenyl ether, glycidyl 2-methylphenyl ether,isophorone oxide, α-Pinene oxide, cis-stilbene oxide, styrene oxide,Methyl,Methyl 7-oxabicyclo[4.1.0]heptane-3-carboxylate, 22-Ethylhexyl7-oxabicyclo(4.1.0)heptane-3-carboxylate,3-ethyl-3-hydroxymethyloxetane,3-ethyl-3-(3-hydroxypropyl)oxymethyloxetane, or3-ethyl-3-(4-hydroxybutyl)oxymethyloxetane. 15) A method of forming athree-dimensional object comprising the steps of: a. forming a layer ofthe composition according to any one of the preceding claims, b. curingthe layer with electromagnetic radiation in order to form a desiredshape, and c. repeating the steps of forming and curing a plurality oftimes to obtain a three-dimensional object.